CN116060053A - Method for regenerating catalyst to be regenerated and method for recovering activity of catalyst to be regenerated - Google Patents
Method for regenerating catalyst to be regenerated and method for recovering activity of catalyst to be regenerated Download PDFInfo
- Publication number
- CN116060053A CN116060053A CN202111274373.4A CN202111274373A CN116060053A CN 116060053 A CN116060053 A CN 116060053A CN 202111274373 A CN202111274373 A CN 202111274373A CN 116060053 A CN116060053 A CN 116060053A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- regenerated
- temperature
- acid
- procatalyst
- 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
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- 238000000034 method Methods 0.000 title claims abstract description 67
- 230000000694 effects Effects 0.000 title claims abstract description 58
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 9
- 238000011069 regeneration method Methods 0.000 claims abstract description 36
- 238000011084 recovery Methods 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 230000008929 regeneration Effects 0.000 claims abstract description 20
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- 238000010438 heat treatment Methods 0.000 claims description 58
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- 238000009826 distribution Methods 0.000 claims description 31
- 238000010304 firing Methods 0.000 claims description 29
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000223 polyglycerol Polymers 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
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- 239000000811 xylitol Substances 0.000 claims description 4
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 4
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- 235000010447 xylitol Nutrition 0.000 claims description 4
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
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- 238000006243 chemical reaction Methods 0.000 description 16
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
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- 238000005470 impregnation Methods 0.000 description 12
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 12
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Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/285—Regeneration or reactivation of catalysts comprising compounds of phosphorus
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
- B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/701—Use of spent catalysts
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Abstract
The invention relates to the technical field of catalyst regeneration, and discloses a regeneration method of a catalyst to be regenerated and an activity recovery method of the catalyst to be regenerated. The method comprises the following steps: (1) Determining the peak-out result of substances to be removed in the catalyst to be regenerated by a programmed temperature oxidation method; (2) And (3) according to the peak-out result measured in the step (1), carrying out temperature programming roasting on the catalyst to be regenerated. According to the method for regenerating the catalyst, provided by the invention, the catalyst to be regenerated is subjected to sectional roasting according to the peak outlet temperature of the substance to be removed of the catalyst to be regenerated in the test result of the temperature programming oxidation method, so that the decomposition of each component in the catalyst to be regenerated can be promoted, the excessive roasting or the insufficient roasting can be prevented, and the activity recovery degree of the regenerated catalyst is improved.
Description
Technical Field
The invention relates to the technical field of catalyst regeneration, in particular to a regeneration method of a catalyst to be regenerated and an activity recovery method of the catalyst to be regenerated.
Background
The hydrogenation catalyst plays an important role in the production process of producing clean fuel, and can remove impurities in raw oil. However, in the use process, the activity of the hydrogenation catalyst is gradually reduced, and the reaction temperature is continuously increased until the upper operating temperature limit of the device is reached. After deactivation of the hydrogenation catalyst, a regeneration step is required to restore its activity. Increasing the activity of the catalyst can extend the operating cycle of the device. Thus, the extent to which the spent catalyst activity is restored directly affects the lifetime of the reuse. Therefore, it is necessary to develop a technique for regenerating the deactivated catalyst to promote the reuse effect of the hydrogenation catalyst.
The types of hydrogenation catalysts are numerous, and the deactivation and regeneration methods of different catalysts are different. The deactivated catalyst contains carbon deposit and is regenerated through high temperature roasting. This regeneration method has general advantages, but the efficiency of this regeneration method is also somewhat deficient. For the deactivated catalyst with a special pore structure, if the catalyst is directly regenerated at high temperature, the problems of incomplete roasting or excessive roasting are easily generated, the regeneration effect of the catalyst is not easy to control, and the optimal regeneration effect is not achieved.
Aiming at the defects of the prior art, a regeneration method and an activity recovery method of a hydrogenation catalyst are provided, and the effect of promoting the activity recovery of the hydrogenation catalyst is promoted.
Disclosure of Invention
The invention aims to solve the problems of incomplete roasting or excessive roasting in a high-temperature roasting regeneration method, and provides a regeneration method of a catalyst to be regenerated and an activity recovery method of the catalyst to be regenerated. The method can prevent over-roasting or under-roasting and improve the activity recovery degree of the regenerated catalyst.
In order to achieve the above object, a first aspect of the present invention provides a method for regenerating a catalyst, the method comprising the steps of:
(1) Determining the peak-out result of substances to be removed in the catalyst to be regenerated by a programmed temperature oxidation method;
(2) And (3) according to the peak-out result measured in the step (1), carrying out temperature programming roasting on the catalyst to be regenerated.
A second aspect of the present invention provides a method for recovering the activity of a catalyst to be regenerated, the method comprising: the regeneration method according to the first aspect of the present invention regenerates the catalyst to be regenerated to obtain a regenerated catalyst, then contacts the regenerated catalyst with an aqueous solution of an organic alcohol compound and/or a carboxylic acid compound, and then dries to obtain a catalyst with recovered activity.
Through the technical scheme, the beneficial technical effects obtained by the invention are as follows:
1) According to the method for regenerating the catalyst, provided by the invention, the catalyst to be regenerated is subjected to sectional roasting according to the peak outlet temperature of the substances to be removed in the catalyst to be regenerated in the test result of the temperature programming oxidation method, so that the decomposition of each component in the catalyst to be regenerated can be promoted, the excessive roasting or the insufficient roasting can be prevented, and the activity recovery degree of the regenerated catalyst is improved;
2) According to the method for recovering the activity of the catalyst to be regenerated, the activity of the catalyst can be further recovered by supplementing the regenerated catalyst with the organic alcohol compound and/or the carboxylic acid compound.
Drawings
FIG. 1 is a graph showing the results of the temperature-programmed oxidation method for the catalyst to be regenerated in example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, when not specifically described, the 2-6nm hole means a hole having a diameter of 2nm or more and less than 6nm, the 2-4nm hole means a hole having a diameter of 2nm or more and less than 4nm, the 4-6nm hole means a hole having a diameter of 4nm or more and less than 6nm, and the 8-20nm hole means a hole having a diameter of 8nm or more and less than 20nm.
The first aspect of the present invention provides a method for regenerating a catalyst to be regenerated, wherein the method comprises the steps of:
(1) Determining the peak-out result of substances to be removed in the catalyst to be regenerated by a programmed temperature oxidation method;
(2) And (3) according to the peak-out result measured in the step (1), carrying out temperature programming roasting on the catalyst to be regenerated.
In step (1):
in a preferred embodiment of the invention, in the temperature-programmed oxidation process, the carrier gas is selected from an oxygen-containing gas selected from air and/or oxygen, preferably air.
In a preferred embodiment of the present invention, in the temperature-programmed oxidation method, the flow rate of the carrier gas is 30 to 200mL/min, preferably 50 to 150mL/min.
In one embodiment of the present invention, in the temperature-programmed oxidation method, the temperature is raised from room temperature to 500-800 ℃ at a temperature-raising rate of 1-15 ℃/min. The room temperature is not particularly limited, and may be 10-35 ℃.
In a preferred embodiment of the present invention, the specific illustration of the catalyst to be regenerated is not particularly limited, and may be various catalysts to be regenerated in the conventional sense in the art, the illustration of which corresponds to a procatalyst (may also be referred to as a fresh catalyst). In a preferred embodiment of the present invention, any non-fresh catalyst that can be regenerated by calcination (i.e., a catalyst after reaction) can be regenerated using the regeneration process of the present invention.
In a preferred embodiment of the invention, the procatalyst of the catalyst to be regenerated comprises at least one group VIII metal element, at least one group VIB metal element, optionally phosphorus pentoxide, and a support alumina, and the procatalyst pore diameter of the catalyst to be regenerated exhibits a bimodal pore distribution in the range of 2-6nm and 8-20nm.
In the invention, the pore diameter of the procatalyst shows bimodal pore distribution in the range of 2-6nm and 8-20nm, which means that the pore diameter distribution of the procatalyst shows two peaks in the pore diameter range of 2-6nm and 8-20nm. Typically, the support also has a certain number of pore size distributions at 2-6nm, but this portion of the pores of the support do not peak and do not form bimodal pores.
In a preferred embodiment of the present invention, the group VIII metal element includes, but is not limited to, at least one of Fe, co, ni, ru, pt and Pd, preferably Co and/or Ni.
In a preferred embodiment of the present invention, the group VIB metal element includes, but is not limited to, at least one of Cr, mo, and W, preferably Mo and/or W.
In a preferred embodiment of the present invention, a process for preparing the sameThe water absorption of the alumina raw material of the catalyst is more than 0.9mL/g, preferably 0.9-1.2mL/g; preferably, the specific surface area of the alumina raw material is more than 260m 2 Preferably 260-400m 2 /g; preferably, the average pore diameter of the alumina raw material is more than 8nm, more preferably 8-14nm, and the pore distribution form is unimodal pore distribution; preferably, in the alumina raw material, the pore volume with the pore diameter distribution of 2-6nm accounts for not more than 10%, more preferably not more than 8%, still more preferably 5-8% of the total pore volume of the alumina raw material; in a particularly preferred case, the pore volume of the alumina raw material having a pore size distribution of 2 to 4nm is not more than 4%, more preferably not more than 2%, of the total volume of the alumina raw material.
In a preferred embodiment of the present invention, the procatalyst has a specific surface area of 130 to 170m 2 /g。
In a preferred embodiment of the invention, the procatalyst has an average pore diameter of 6 to 18nm, preferably 8 to 10nm.
In a preferred embodiment of the invention, the procatalyst has a pore volume of 0.2 to 0.4cm 3 Preferably 0.25-0.4 cm/g 3 /g。
In a preferred embodiment of the invention, the pore volume with a pore size distribution of from 2 to 6nm represents from 8 to 15%, more preferably from 9 to 12%, of the total volume of the procatalyst.
Wherein, the determination of the specific surface area, pore volume, pore distribution and average pore diameter of the raw catalyst in the invention refers to the determination of the catalyst after roasting for 3 hours at 400 ℃. The specific surface area, pore distribution, average pore diameter and pore volume of the procatalyst were measured by the low temperature nitrogen adsorption method (BET) (see "petrochemical analysis method (RIPP test method)", yang Cuiding et al, scientific Press, 1990). Wherein the pore volume of 2-100nm is calculated according to BET results.
In a preferred embodiment of the present invention, the procatalyst composition is as defined in (Xi ai )·(Yi bi )·(Zi ci ) Sup, where Xi is the group VIB metal oxide, ai is the mass of Xi relative to 1 g of support Xi, and Yi is the group VIII metal oxideBi is the mass relative to 1 g of the support Yi and Zi is P 2 O 5 Ci is 1 g of carrier P 2 O 5 Sup refers to the mass of the support in the catalyst, calculated as 1 gram, which satisfies the following conditions: (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup Has a value of 0.4 to 0.9nm, preferably 0.5 to 0.8nm, ρ Xi 、ρ Yi 、ρ Zi Respectively a group VIB metal oxide, a group VIII metal oxide and P 2 O 5 Density, SA of sup Is the specific surface area of the carrier. Wherein the specific surface area of the support refers to the specific surface area of the alumina raw material in the raw material for preparing the procatalyst. ρMoO 3 、ρWO 3 、ρNiO、ρCoO、ρP 2 O 5 According to the proportion of 4.69g/cm 3 、7.16g/cm 3 、6.67g/cm 3 、6.45g/cm 3 And 2.39g/cm 3 And (5) calculating.
In a preferred embodiment of the present invention, the molar ratio Zi/Xi in the procatalyst is 0.05-0.3, more preferably 0.08-0.2.
In a preferred embodiment of the invention, the atomic concentration of the group VIB metal element in the procatalyst at the surface of the support is from 5 to 13atom/nm 2 Preferably 5-11 atoms/nm 2 。
In the invention, the atomic concentration of the group VIB metal element on the surface of the carrier refers to the average atomic concentration of the group VIB metal element on the surface of the carrier, and the average atomic concentration is obtained by measuring the metal loading and calculating the specific surface area of the carrier, specifically, the average atomic concentration can be obtained by the following calculation: atomic concentration= (ai/M Xi )×N A /(1×SA sup ) Wherein N is A For the Avoder constant, ai is the mass relative to 1 gram of carrier Xi, M Xi Molecular weight of Xi, SA sup Is the specific surface area of the carrier.
In a preferred embodiment of the present invention, the atomic ratio of the group VIII metal element to the total of the group VIII metal element and the group VIB metal element in the procatalyst is 0.05 to 0.35, preferably 0.1 to 0.3.
In a preferred embodiment of the present invention, the procatalyst has an equivalent diameter of 0.5 to 1.8mm, more preferably 0.8 to 1.6mm. In the present invention, the shape of the procatalyst is not particularly limited, and any shape of a catalyst conventional in the art is suitable for the present invention. Preferably, the shape of the catalyst is cylindrical, clover, butterfly, honeycomb or other irregular shape, more preferably butterfly.
In a preferred embodiment of the invention, the catalyst further comprises one or more organic alcohol compounds and/or carboxylic acid compounds in a molar ratio of organic alcohol compounds and/or carboxylic acid compounds to group VIII metal element of 1 to 6, preferably 2 to 5.
The organic alcohol compound may be at least one of monohydric alcohol, dihydric alcohol and polyhydric alcohol. In a preferred case, the organic alcohol compound is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol, ethylene glycol, glycerol, butanetetraol, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol and trimethylolethane, preferably at least one of glycerol, propanol and ethylene glycol.
In a preferred case, the carboxylic acid compound is selected from one or more of formic acid, acetic acid, propionic acid, citric acid, caprylic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, caproic acid, capric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, capric acid, stearic acid and tartaric acid, preferably at least one of formic acid, citric acid and acetic acid.
In a particularly preferred case, the procatalyst further comprises one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol, ethylene glycol, glycerol, tetrol, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol, trimethylolethane and/or formic acid, acetic acid, propionic acid, citric acid, octanoic acid, adipic acid, malonic acid, succinic acid, maleic acid, pentanoic acid, hexanoic acid, decanoic acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, pentanoic acid, hexanoic acid, decanoic acid, octadecanoic acid, tartaric acid.
In a preferred embodiment of the present invention, the substance to be removed includes at least one of carbon deposit, sulfide, and nitrogen-containing organic matter.
In a preferred embodiment of the present invention, the component to be removed includes char and sulfide.
In a preferred embodiment of the present invention, the catalyst to be regenerated has a carbon content of 1 to 10wt% and a sulfur content of 1 to 20wt%. Wherein the carbon and sulfur contents are based on the mass of the element.
In step (2):
in a preferred embodiment of the present invention, the number of peaks n and the peak output temperature T of each peak are determined based on the peak output results i The method comprises the steps of carrying out a first treatment on the surface of the Where i is an integer from 1 to n.
In the present invention, when the temperature programmed oxidation test is performed on the catalyst to be regenerated, if the difference between the peak temperatures of two adjacent peaks is within 10 ℃, the peak temperature can be regarded as one peak, and the peak temperature is the average value of the peak temperatures of the two peaks.
In a preferred embodiment of the present invention, in the firing temperature-increasing program of the temperature-programmed firing, the temperature-increasing program in the firing temperature-increasing program is divided into n segments according to the peak-exiting result, and the final temperature in each segment of the firing temperature-increasing program corresponds to T in turn i 。
In a preferred embodiment of the invention, the temperature rise rate in each stage of the firing temperature rise program is independently selected from 1 to 20 ℃/min, preferably 2 to 15 ℃/min.
In a preferred embodiment of the invention, the constant temperature time of the final temperature in each firing temperature increase program is independently selected from 1 to 10 hours, preferably 3 to 6 hours.
In a preferred embodiment of the present invention, the temperature increase rate in the first-stage firing temperature increase program is not less than the temperature increase rate in the second-stage firing temperature increase program to the nth-stage firing temperature increase program.
In a preferred embodiment of the present invention, the temperature increase rate is sequentially decreased in the first-stage firing temperature increase routine to the N-th-stage firing temperature increase routine. Further preferably, between adjacent roasting heating program sections, the heating rate is sequentially decreased by 1-10 ℃/min, preferably sequentially decreased by 2-7 ℃/min.
In the invention, the regeneration effect can be further improved and the activity recovery degree of the regenerated catalyst can be improved by controlling the temperature rising rate of each stage of roasting.
In a preferred embodiment of the present invention, in the firing temperature-raising routine, the firing temperature-raising routine further includes an n+1th stage, and in the n+1th stage firing temperature-raising routine, the temperature is raised to T n +10 ℃ to T n +50 ℃, preferably up to T n +15℃ to T n Roasting at +30℃.
In a preferred embodiment of the present invention, the temperature increase rate in the n+1st stage firing temperature increase program is 1 to 10 ℃/min, preferably 1 to 5 ℃/min.
In a preferred embodiment of the present invention, the constant temperature time in the n+1st stage firing temperature increase program is 1 to 5 hours, preferably 2 to 4 hours.
Wherein the inventors of the present invention have found that, at T n After constant temperature roasting at the temperature, continuously raising the temperature and roasting for a period of time, so that the regeneration activity of the regenerated catalyst can be further improved.
In a preferred embodiment of the present invention, the temperature-programmed firing is performed under an air atmosphere.
A second aspect of the present invention provides a method for recovering the activity of a catalyst to be regenerated, the method comprising:
the regeneration method according to the first aspect of the present invention regenerates the catalyst to be regenerated to obtain a regenerated catalyst, then contacts the regenerated catalyst with an aqueous solution of an organic alcohol compound and/or a carboxylic acid compound, and then dries to obtain a catalyst with recovered activity.
In a preferred embodiment of the present invention, the procatalyst of the catalyst to be regenerated contains an organic alcohol compound and/or a carboxylic acid compound.
In a preferred embodiment of the present invention, the organic alcohol compound is selected from one or more selected from methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol, ethylene glycol, glycerol, tetrol, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol and trimethylolethane, preferably at least one of glycerol, propanol and ethylene glycol.
In a preferred embodiment of the present invention, the carboxylic acid compound is selected from one or more selected from formic acid, acetic acid, propionic acid, citric acid, caprylic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, caproic acid, capric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, capric acid, stearic acid and tartaric acid, preferably at least one of formic acid, citric acid and acetic acid.
In a preferred embodiment of the present invention, the organic alcohol compound and/or carboxylic acid compound is the same species as the organic alcohol compound and/or carboxylic acid compound in the procatalyst.
In a preferred embodiment of the present invention, the organic alcohol compound and/or carboxylic acid compound is added in an amount of 0.5 to 2 times, preferably 0.75 to 1.5 times the content of the organic alcohol compound and/or carboxylic acid compound in the procatalyst.
The present invention will be described in detail by examples.
The amount of feed during the preparation of the procatalyst is determined according to the specific exemplary illustrations given herein.
Exemplary description: (1) Determining the feeding amount of the group VIB metal precursor in each g of the carrier according to the atomic concentration of the group VIB metal element and the specific surface area of the carrier (alumina); (2) Determining the amount of the group VIII metal precursor per g of carrier according to the atomic ratio of the group VIII metal element to the total amount of the group VIII metal element and the group VIB metal element; (3) According to (ai/ρ Xi +bi/ρ Yi +ci/ρ Zi )/SA sup To calculate P 2 O 5 Further determining the amount of phosphorus-containing compound per g of carrier; (4) Based on the mole of the organic alcohol compound and/or carboxylic acid compound and the group VIII metal elementCalculating the ratio of the organic alcohol compound and/or carboxylic acid compound; (5) According to the feeding amounts of the VIB group metal precursor, the VIII group metal precursor, the phosphorus-containing compound and the organic alcohol compound and/or the carboxylic acid compound, impregnating alumina by using an impregnating solution according to a pore saturated impregnation method, and then drying. Specifically, firstly dissolving a phosphorus-containing compound in water, then adding an organic alcohol compound and/or a carboxylic acid compound, a VIB group metal precursor and a VIII group metal precursor, stirring under heating until the phosphorus-containing compound is completely dissolved, and keeping the temperature constant to obtain an impregnating solution; (6) Measuring the water absorption of the carrier, and calculating the liquid absorption of the carrier according to the formula of the water absorption-0.1 of the carrier; (7) According to the liquid absorption rate of the carrier, the impregnating solution is fixed to a corresponding volume (the liquid absorption rate of the carrier is multiplied by the mass of the carrier), and the impregnating solution and the carrier with corresponding mass are uniformly mixed and kept stand, and then dried, so that the catalyst is prepared.
In the following examples, the composition of the catalyst was calculated from the amount of the feed. The specific surface area, pore distribution, pore diameter and pore volume of the catalyst and the carrier of 2-100nm are measured by a low-temperature nitrogen adsorption method (see the methods of petrochemical analysis (RIPP test method), yang Cuiding et al, scientific Press, 1990). The sulfur mass fraction in the product was analyzed by a sulfur-nitrogen analyzer (model TN/TS3000, manufactured by Siemens, inc.), and the content of aromatic hydrocarbon was analyzed by near infrared spectroscopy.
The hydrodesulfurization performance of the catalyst is measured on a 20mL high-pressure micro-reactor, and the oxidation state catalyst is directly converted into a sulfidation state catalyst by adopting a temperature programming sulfidation method. The vulcanization conditions are as follows: the vulcanization pressure is 6.4MPa, and the vulcanized oil contains CS 2 2wt% kerosene, volume space velocity 2 hours -1 The hydrogen-oil volume ratio is 300v/v, the constant temperature is kept for 6 hours at 230 ℃/h, then the temperature is raised to 360 ℃ for 8 hours of vulcanization, and the temperature raising rate of each stage is 10 ℃/h. And after vulcanization, switching the reaction raw materials for carrying out hydrodesulfurization activity test, wherein the sulfur content of the reaction raw materials is 10890ppm, and the aromatic hydrocarbon content is 39.0wt% of high aromatic hydrocarbon distillate oil. The test conditions were: the pressure is 6.4MPa, and the volume space velocity is 1.5h -1 The hydrogen-oil volume ratio was 300v/v and the reaction temperature was 340 ℃.
The temperature programming oxidation method is carried out on a thermogravimetric mass spectrometry (NETZSCH STA 409 PC/PG) instrument, and the specific operation conditions are as follows: taking air as carrier gas, wherein the flow rate of the carrier gas is 50mL/min, heating the sample from room temperature to 600 ℃ at the heating rate of 10 ℃/min, performing temperature programming oxidation test, and monitoring at the instrument gas outlet by using a mass spectrometer, thereby obtaining the curve of the decomposition product of the sample along with the temperature change.
The activity of the catalyst is defined as the hydrodesulfurization reaction rate constant (k HDS ) The reaction series is calculated according to the 1.2 level, and the calculation formula is as follows: k (k) HDS ＝1/(n-1)×(s p (1-n) -s f (1-n) ) X LHSV, where n is the reaction rate constant, S p S is the sulfur content in the product f Is the sulfur content in the raw material.
The degree of recovery of the catalyst activity is defined as: the ratio of the hydrodesulfurization reaction rate constant of the regenerated catalyst to the hydrodesulfurization reaction rate constant of the fresh catalyst is x 100%.
Example 1
(1) Preparation of procatalyst
Selecting a gamma-alumina carrier, wherein the water absorption rate is 0.98mL/g, and the specific surface area is 280m 2 And/g, wherein the average pore diameter is 10.7nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 8%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 4%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and glycerol into phosphoric acid aqueous solution, heating and stirring at 85 ℃ for 2 hours until the basic nickel carbonate and the glycerol are completely dissolved, and keeping the temperature for 3 hours to obtain the impregnation liquid containing the active metal components. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
the atomic concentration of Mo in the catalyst was 7atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.29, P 2 O 5 /MoO 3 The molar ratio was 0.13, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup 0.5nm, glycerol andthe molar ratio of Ni was 2.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 165m 2 Per gram, pore volume of 0.38cm 3 And/g, wherein the average pore diameter is 9.2nm, the pore structure is characterized by bimodal pore distribution at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 9.2%.
(2) Catalyst testing
And (3) performing hydrodesulfurization performance test on the prepared catalyst, stopping the reaction after 30 days of operation, and unloading the reacted catalyst to obtain the catalyst to be regenerated. Wherein the substances to be removed of the catalyst to be regenerated comprise carbon deposit and sulfide, and the carbon and sulfur content of the catalyst to be regenerated is 6.8wt% and 10.5wt%, respectively.
(3) Regeneration of catalyst to be regenerated
And (3) carrying out a temperature programming oxidation method test on the catalyst to be regenerated, wherein the peak output number of substances to be removed of the catalyst to be regenerated is determined to be 2, the peak output temperature of the first peak is 340 ℃, the peak output temperature of the second peak is 440 ℃, and the third temperature is 450 ℃.
Placing the catalyst to be regenerated in a muffle furnace, performing programmed heating roasting under an air atmosphere, heating from room temperature to 340 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 5 hours, heating to 445 ℃ at a heating rate of 5 ℃ min, keeping the temperature for 5 hours, heating to 470 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 4 hours to obtain the regenerated catalyst;
and uniformly mixing the regenerated catalyst with glycerol aqueous solution by adopting an isovolumetric impregnation method, and drying at 130 ℃ for 3 hours to obtain the catalyst with recovered activity. Wherein the glycerol consumption is 1.5 times of the glycerol content in the procatalyst.
The activity recovery degree of the catalyst after the hydrodesulfurization performance test was again carried out was 96%.
Example 2
(1) Preparation of procatalyst
Selecting a gamma-alumina carrier, wherein the water absorption rate is 0.98mL/g, and the specific surface area is 280m 2 Per g, average pore diameter of 10.7nm, pore diameter of 2-6nThe proportion of the pore volume of m to the total pore volume is 8%, the proportion of the pore volume of pore diameter of 2-4nm to the total pore volume is 4%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and glycerol into phosphoric acid aqueous solution, heating and stirring at 90 ℃ for 3 hours until the basic nickel carbonate and the glycerol are completely dissolved, and keeping the temperature for 3 hours to obtain an impregnation liquid containing active metals. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
the atomic concentration of Mo in the catalyst was 11atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.2, P 2 O 5 /MoO 3 Molar ratio of 0.1, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 5at 0.72 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 151m 2 Per gram, pore volume of 0.32cm 3 And/g, wherein the average pore diameter is 8.5nm, the pore structure is characterized by bimodal pore distribution at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 9%.
(2) Catalyst testing
And (3) performing hydrodesulfurization performance test on the prepared catalyst, stopping the reaction after 30 days of operation, and unloading the reacted catalyst to obtain the catalyst to be regenerated. Wherein the substances to be removed of the catalyst to be regenerated comprise carbon deposit and sulfide, and the carbon and sulfur content of the catalyst to be regenerated is 7.6wt% and 12.3wt%, respectively.
(3) Regeneration of catalyst to be regenerated
And (3) carrying out a temperature programming oxidation method test on the catalyst to be regenerated, and determining that the peak output of substances to be removed of the catalyst to be regenerated is 2, wherein the peak output temperature of the first peak is 340 ℃, and the peak output temperature of the second peak is 430 ℃.
Placing a catalyst to be regenerated in a muffle furnace, performing programmed heating roasting in an air atmosphere, heating from room temperature to 340 ℃ at a heating rate of 8 ℃/min, keeping the temperature for 5 hours, heating to 430 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, heating to 460 ℃ at a heating rate of 1.5 ℃/min, and keeping the temperature for 4 hours to obtain the regenerated catalyst;
and uniformly mixing the regenerated catalyst with glycerol aqueous solution by adopting an isovolumetric impregnation method, and drying at 130 ℃ for 3 hours to obtain the catalyst with recovered activity. Wherein the glycerol consumption is 0.8 times of the glycerol content in the procatalyst.
The degree of activity recovery after the catalyst recovered in activity was subjected to hydrodesulfurization performance test again was 94%.
Example 3
(1) Preparation of procatalyst
Selecting a gamma-alumina carrier, wherein the water absorption rate is 0.98mL/g, and the specific surface area is 280m 2 And/g, wherein the average pore diameter is 10.7nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 8%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 4%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and glycerol into phosphoric acid aqueous solution, heating and stirring at 90 ℃ for 3 hours until the basic nickel carbonate and the glycerol are completely dissolved, and keeping the temperature for 3 hours to obtain the impregnation liquid containing the active metal components. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 2 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
the atomic concentration of Mo in the catalyst is 8atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.28, P 2 O 5 /MoO 3 Molar ratio of 0.2, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of glycerol to Ni was 3at 0.623 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 164m 2 Per gram, pore volume of 0.35cm 3 Per g, the average pore diameter is 8.5nm, the pore structure is characterized by bimodal pore distribution at 2-6nm and 8-20nm, and the pore volume is 2-6nmThe proportion of the total pore volume.
(2) Catalyst testing
And (3) performing hydrodesulfurization performance test on the prepared catalyst, stopping the reaction after 30 days of operation, and unloading the reacted catalyst to obtain the catalyst to be regenerated. Wherein the substances to be removed of the catalyst to be regenerated comprise carbon deposit and sulfide, and the carbon and sulfur content of the catalyst to be regenerated is 6.5wt% and 10.2wt%, respectively.
(3) Regeneration of catalyst to be regenerated
And (3) carrying out a temperature programming oxidation method test on the catalyst to be regenerated, and determining that the peak output of substances to be removed of the catalyst to be regenerated is 2, wherein the peak output temperature of the first peak is 320 ℃, and the peak output temperature of the second peak is 440 ℃.
Placing a catalyst to be regenerated in a muffle furnace, performing programmed heating roasting in an air atmosphere, heating from room temperature to 320 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 5 hours, heating to 440 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, heating to 470 ℃ at a heating rate of 1.5 ℃/min, and keeping the temperature for 4 hours to obtain the regenerated catalyst;
and uniformly mixing the regenerated catalyst with glycerol aqueous solution by adopting an isovolumetric impregnation method, and drying at 130 ℃ for 3 hours to obtain the catalyst with recovered activity. Wherein the glycerol consumption is 1.2 times of the glycerol content in the procatalyst.
The activity recovery degree of the catalyst after the hydrodesulfurization performance test was again carried out was 96%.
Example 4
(1) Preparation of procatalyst
Selecting a gamma-alumina carrier, wherein the water absorption rate is 0.98mL/g, and the specific surface area is 280m 2 And/g, wherein the average pore diameter is 10.7nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 8%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 4%, and the pore diameter distribution is mainly concentrated at 8-20nm.
Respectively adding ammonium metatungstate, basic nickel carbonate and citric acid into a phosphoric acid aqueous solution, heating and stirring for 2 hours at 90 ℃ until the ammonium metatungstate, the basic nickel carbonate and the citric acid are completely dissolved, and keeping the temperature for 3 hours to obtain an impregnating solution containing active metal components. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 2 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 3 hours at 130 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
w in the catalyst had an atomic concentration of 5atom/nm 2 Ni/(Ni+W) atomic ratio of 0.3, P 2 O 5 /WO 3 Molar ratio of 0.2, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of citric acid to Ni was 2 at 0.407 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 162m 2 Per gram, pore volume of 0.39cm 3 And/g, wherein the average pore diameter is 9.6nm, the pore structure is characterized by bimodal pore distribution at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 10.5%.
(2) Catalyst testing
And (3) performing hydrodesulfurization performance test on the prepared catalyst, stopping the reaction after 30 days of operation, and unloading the reacted catalyst to obtain the catalyst to be regenerated. Wherein the substances to be removed of the catalyst to be regenerated comprise carbon deposit and sulfide, and the carbon and sulfur content of the catalyst to be regenerated is 6.4wt% and 7.8wt%, respectively.
(3) Regeneration of catalyst to be regenerated
And (3) carrying out a temperature programming oxidation method test on the catalyst to be regenerated, and determining that the peak output of substances to be removed of the catalyst to be regenerated is 2, wherein the peak output temperature of the first peak is 300 ℃, and the peak output temperature of the second peak is 455 ℃.
Placing the catalyst to be regenerated in a muffle furnace, performing programmed heating roasting under an air atmosphere, heating from room temperature to 300 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 5 hours, heating to 455 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, heating to 470 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 4 hours to obtain the regenerated catalyst;
and uniformly mixing the regenerated catalyst with a citric acid aqueous solution by adopting an isovolumetric impregnation method, and drying at 130 ℃ for 3 hours to obtain the catalyst with recovered activity. Wherein the amount of the citric acid is 1.5 times of the content of the citric acid in the procatalyst.
The activity recovery degree of the catalyst after the hydrodesulfurization performance test was carried out again was 97%.
Example 5
(1) Preparation of procatalyst
Selecting a gamma-alumina carrier, wherein the water absorption rate is 1.04mL/g, and the specific surface area is 270m 2 And/g, wherein the average pore diameter is 11.7nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 5%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 1%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and citric acid into phosphoric acid aqueous solution, heating and stirring at 85 ℃ for 3 hours until the basic nickel carbonate and the citric acid are completely dissolved, and keeping the temperature for 2 hours to obtain the impregnation liquid containing the active metal components. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
the atomic concentration of Mo in the catalyst is 9atom/nm 2 Ni/(Ni+Mo) atomic ratio of 0.25, P 2 O 5 /MoO 3 Molar ratio of 0.12, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of citric acid to Ni was 2 at 0.62 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 154m 2 Per gram, pore volume of 0.36cm 3 And/g, wherein the average pore diameter is 9.4nm, the pore structure is characterized by bimodal pore distribution at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 9.8%.
(2) Catalyst testing
And (3) performing hydrodesulfurization performance test on the prepared catalyst, stopping the reaction after 30 days of operation, and unloading the reacted catalyst to obtain the catalyst to be regenerated. Wherein the substances to be removed of the catalyst to be regenerated comprise carbon deposit and sulfide, and the carbon and sulfur content of the catalyst to be regenerated is 7.4wt% and 11.1wt%, respectively.
(3) Regeneration of catalyst to be regenerated
And (3) carrying out a temperature programming oxidation method test on the catalyst to be regenerated, and determining that the peak output of substances to be removed of the catalyst to be regenerated is 2, wherein the peak output temperature of the first peak is 340 ℃, and the peak output temperature of the second peak is 420 ℃.
Placing the catalyst to be regenerated in a muffle furnace, performing programmed heating roasting under an air atmosphere, heating from room temperature to 340 ℃ at a heating rate of 6 ℃/min, keeping the temperature for 5 hours, heating to 420 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, heating to 460 ℃ at a heating rate of 1 ℃/min, and keeping the temperature for 4 hours to obtain the regenerated catalyst;
and uniformly mixing the regenerated catalyst with a citric acid aqueous solution by adopting an isovolumetric impregnation method, and drying at 150 ℃ for 3 hours to obtain the catalyst with recovered activity. Wherein the amount of the citric acid is 1 time of the content of the citric acid in the procatalyst.
The degree of activity recovery after the catalyst recovered in activity was subjected to hydrodesulfurization performance test again was 94%.
Example 6
(1) Preparation of procatalyst
Selecting a gamma-alumina carrier, wherein the water absorption rate is 1.04mL/g, and the specific surface area is 270m 2 And/g, wherein the average pore diameter is 11.7nm, the proportion of pore volume with the pore diameter of 2-6nm to the total pore volume is 5%, the proportion of pore volume with the pore diameter of 2-4nm to the total pore volume is 1%, and the pore diameter distribution is mainly concentrated at 8-20nm.
MoO is carried out 3 Respectively adding basic nickel carbonate and citric acid into phosphoric acid aqueous solution, heating and stirring at 95 ℃ for 3 hours until the basic nickel carbonate and the citric acid are completely dissolved, and keeping the temperature for 2 hours to obtain the impregnation liquid containing the active metal components. The impregnating solution and the carrier are uniformly mixed and then are kept stand for 3 hours, and the catalyst with the particle size of 1.6mm and the shape of a butterfly is prepared by drying for 5 hours at 120 ℃.
The carrier and the components are used in such amounts that the catalyst prepared satisfies the following conditions:
the atomic concentration of Mo in the catalyst is 10atom/nm 2 Ni/(Ni+Mo) atomic ratio0.28, P 2 O 5 /MoO 3 Molar ratio of 0.27, (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup The molar ratio of citric acid to Ni was 2 at 0.85 nm.
The catalyst was calcined at 400 c for 3 hours and analyzed for pore size distribution using a low temperature nitrogen adsorption method. The specific surface area of the catalyst was 135m 2 Per gram, pore volume of 0.27cm 3 And/g, wherein the average pore diameter is 8.0nm, the pore structure is characterized by bimodal pore distribution at 2-6nm and 8-20nm, and the proportion of the pore volume with the pore diameter of 2-6nm to the total pore volume is 12.5%.
(2) Catalyst testing
And (3) performing hydrodesulfurization performance test on the prepared catalyst, stopping the reaction after 30 days of operation, and unloading the reacted catalyst to obtain the catalyst to be regenerated. Wherein the substances to be removed of the catalyst to be regenerated comprise carbon deposit and sulfide, and the carbon and sulfur content of the catalyst to be regenerated is 6.2wt% and 11.8wt%, respectively.
(3) Regeneration of catalyst to be regenerated
And (3) carrying out a temperature programming oxidation method test on the catalyst to be regenerated, and determining that the peak output of substances to be removed of the catalyst to be regenerated is 2, wherein the peak output temperature of the first peak is 330 ℃, and the peak output temperature of the second peak is 425 ℃.
Placing a catalyst to be regenerated in a muffle furnace, performing programmed heating roasting in an air atmosphere, heating from room temperature to 330 ℃ at a heating rate of 6 ℃/min, keeping the temperature for 5 hours, heating to 425 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5 hours, heating to 465 ℃ at a heating rate of 1.5 ℃/min, and keeping the temperature for 4 hours to obtain the regenerated catalyst;
and uniformly mixing the regenerated catalyst with a citric acid aqueous solution by adopting an isovolumetric impregnation method, and drying at 150 ℃ for 3 hours to obtain the catalyst with recovered activity. Wherein the amount of the citric acid is 1 time of the content of the citric acid in the procatalyst.
The degree of activity recovery after the catalyst recovered in activity was subjected to hydrodesulfurization performance test again was 94%.
Example 7
The same as in example 1, except that the last stage of high temperature calcination was not performed, specifically: in the regeneration of the catalyst to be regenerated in the step (3), the catalyst to be regenerated is placed in a muffle furnace, programmed heating and roasting are carried out under the air atmosphere, the temperature is raised from room temperature to 340 ℃ at a heating rate of 5 ℃/h, the temperature is kept for 5 hours, then the temperature is raised to 445 ℃ at a heating rate of 2 ℃/h, and the temperature is kept for 5 hours, so that the regenerated catalyst is obtained.
The activity recovery degree of the catalyst after activity test was 91.5%.
Example 8
The same as in example 1, except that in the regeneration of the catalyst to be regenerated in step (3), the catalyst to be regenerated was placed in a muffle furnace, temperature programmed calcination was performed under an air atmosphere, the temperature was raised from room temperature to 340℃at a temperature-raising rate of 5℃per minute for 5 hours, then the temperature was raised to 445℃at a temperature-raising rate of 5℃per minute for 5 hours, and finally the temperature was raised to 470℃at a temperature-raising rate of 5℃per minute for 4 hours, to obtain a regenerated catalyst.
The activity of the catalyst recovered was 94.5% after activity test.
Example 9
The same as in example 1, except that in the regeneration of the catalyst to be regenerated in step (3), the catalyst to be regenerated was placed in a muffle furnace, temperature programmed calcination was performed under an air atmosphere, the temperature was raised from room temperature to 340℃at a temperature-raising rate of 2℃per minute for 5 hours, then the temperature was raised to 445℃at a temperature-raising rate of 5℃per minute for 5 hours, and finally the temperature was raised to 470℃at a temperature-raising rate of 10℃per minute for 4 hours, to obtain a regenerated catalyst.
The activity recovery degree of the catalyst after the hydrodesulfurization performance test was again conducted was 88.7%.
Comparative example 1
The same as in example 1, except that in the regeneration of the catalyst to be regenerated in step (3), the catalyst to be regenerated was directly placed in a muffle furnace and heated from room temperature to 470 ℃ at a heating rate of 5 ℃/min under an air atmosphere, and the temperature was maintained for 14 hours.
The activity recovery degree of the catalyst after the hydrodesulfurization performance test was again conducted was 86.2%.
The embodiment and the comparative example show that the invention has better invention effect, the regeneration method of the catalyst and the prepared regenerated catalyst have higher activity and stability, and have good industrial application prospect.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method for regenerating a catalyst to be regenerated, characterized in that it comprises the steps of:
(1) Determining the peak-out result of substances to be removed in the catalyst to be regenerated by a programmed temperature oxidation method;
(2) And (3) according to the peak-out result measured in the step (1), carrying out temperature programming roasting on the catalyst to be regenerated.
2. The regeneration method according to claim 1, wherein in the step (1), the number n of peaks and the peak outlet temperature T of each peak are determined based on the peak outlet result i The method comprises the steps of carrying out a first treatment on the surface of the Where i is an integer from 1 to n.
3. The regeneration method according to claim 1 or 2, wherein in the firing temperature-raising program of the temperature-raising-programmed firing in step (2), the temperature-raising program in the firing temperature-raising program is divided into n segments according to the peak-raising result, the final temperature in each segment of the firing temperature-raising program corresponding to T in turn i ；
Preferably, the temperature rising rate in each stage of roasting temperature rising program is independently selected from 1-20 ℃/min, preferably 2-15 ℃/min;
preferably, the constant temperature time of the final temperature in each stage of roasting temperature rise program is independently selected from 1-10 hours, preferably 3-6 hours;
preferably, the temperature increase rate in the first-stage firing temperature increase program is not less than the temperature increase rate in the second-stage firing temperature increase program to the N-th-stage firing temperature increase program;
preferably, in the first-stage roasting heating program to the nth-stage roasting heating program, the heating rate is sequentially reduced; further preferably, between adjacent roasting heating program sections, the heating rate is sequentially decreased by 1-10 ℃/min, preferably sequentially decreased by 2-7 ℃/min.
4. A regeneration method according to any one of claims 1 to 3, wherein in step (2), in the firing warm-up routine, the firing warm-up routine further includes an n+1th stage, and in the n+1th stage firing warm-up routine, the temperature is raised to T n +10 ℃ to T n Roasting at +50 ℃;
preferably, in the (n+1) -th stage firing temperature-raising program, the temperature-raising rate is 1 to 10 ℃/min, preferably 1 to 5 ℃/min;
preferably, in the (n+1) -th stage firing temperature-raising program, the constant temperature time is 1 to 5 hours, preferably 2 to 4 hours.
5. The regeneration method according to any one of claims 1 to 4, wherein the substance to be removed includes at least one of carbon deposit, sulfide, and nitrogen-containing organic matter;
preferably, the carbon content in the catalyst to be regenerated is 1-10wt% and the sulfur content is 1-20wt%.
6. The regeneration process according to any one of claims 1 to 5, wherein the procatalyst of the catalyst to be regenerated comprises at least one group VIII metal element, at least one group VIB metal element, optionally phosphorus pentoxide, and a support alumina, and has a bimodal pore distribution of pore diameters in the range of 2-6nm and 8-20nm.
7. The regeneration process according to any one of claims 1 to 6, wherein the procatalyst composition of the catalyst to be regenerated is as defined in (Xi ai )·(Yi bi )·(Zi ci ) Sup, where Xi is the group VIB metal oxide, ai is the mass of the group VIII metal oxide relative to 1 gram of support Xi, bi is the mass of the group VIII metal oxide relative to 1 gram of support Yi, zi is P 2 O 5 Ci is relative to 1 g of carrier P 2 O 5 Sup refers to the mass of the support in the catalyst, calculated as 1 gram, which satisfies the following conditions: (ai/ρ) Xi +bi/ρ Yi +ci/ρ Zi )/SA sup Has a value of 0.4 to 0.9nm, preferably 0.5 to 0.8nm, ρ Xi 、ρ Yi 、ρ Zi Respectively a group VIB metal oxide, a group VIII metal oxide and P 2 O 5 Density, SA of sup Is the specific surface area of the carrier;
preferably, the molar ratio Zi/Xi in the procatalyst is 0.05-0.3, preferably 0.08-0.2;
preferably, the atomic concentration of the VIB group metal element in the procatalyst on the surface of the carrier is 5-13atom/nm 2 Preferably 5-11 atoms/nm 2 ；
Preferably, the atomic ratio of the group VIII metal element to the total of the group VIII metal element and the group VIB metal element in the procatalyst is 0.05 to 0.35, preferably 0.1 to 0.3;
preferably, the raw catalyst further comprises one or more organic alcohol compounds and/or carboxylic acid compounds, and the molar ratio of the organic alcohol compounds and/or carboxylic acid compounds to the group VIII metal element is 1 to 6, preferably 2 to 5.
8. A method for recovering the activity of a catalyst to be regenerated, characterized in that the method comprises:
regenerating the catalyst to be regenerated according to the regeneration method of any one of claims 1 to 7 to obtain a regenerated catalyst, then contacting the regenerated catalyst with an aqueous solution of an organic alcohol compound and/or a carboxylic acid compound, and then drying to obtain a catalyst with recovered activity;
preferably, the procatalyst of the catalyst to be regenerated contains an organic alcohol compound and/or a carboxylic acid compound.
9. The activity recovery method according to claim 8, wherein,
the organic alcohol compound is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, amyl alcohol, heptanol, ethylene glycol, glycerol, butyl tetraol, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol and trimethylolethane; preferably, the organic alcohol compound is selected from glycerol and/or propanol;
preferably, the carboxylic acid compound is selected from one or more of formic acid, acetic acid, propionic acid, citric acid, caprylic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, caproic acid, capric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, capric acid, stearic acid and tartaric acid; preferably, the carboxylic acid compound is selected from at least one of formic acid, citric acid and acetic acid.
10. The activity recovery method according to claim 8 or 9, wherein the organic alcohol compound and/or carboxylic acid-based compound is the same type as the organic alcohol compound and/or carboxylic acid-based compound in the procatalyst;
preferably, the organic alcohol compound and/or carboxylic acid compound is added in an amount of 0.5 to 2 times, preferably 0.75 to 1.5 times, the content of the organic alcohol compound and/or carboxylic acid compound in the procatalyst.
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