CN112718019A - Method for recovering activity of hydrocracking catalyst - Google Patents
Method for recovering activity of hydrocracking catalyst Download PDFInfo
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- CN112718019A CN112718019A CN201911030766.3A CN201911030766A CN112718019A CN 112718019 A CN112718019 A CN 112718019A CN 201911030766 A CN201911030766 A CN 201911030766A CN 112718019 A CN112718019 A CN 112718019A
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- catalyst
- active metal
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- roasting
- hydrocracking catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 27
- 230000000694 effects Effects 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 27
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 24
- 230000006315 carbonylation Effects 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000001257 hydrogen Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- -1 acyl anhydride Chemical class 0.000 claims description 2
- 150000001266 acyl halides Chemical class 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 16
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 238000011946 reduction process Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000001502 supplementing effect Effects 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910000480 nickel oxide Inorganic materials 0.000 description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010835 comparative analysis Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- 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
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
-
- 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
-
- 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
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an activity recovery method of a hydrocracking catalyst, which comprises the following steps: (1) reducing the to-be-generated hydrocracking catalyst deposited with metal Ni impurities; (2) carrying out carbonylation treatment on the material subjected to reduction treatment in the step (1) to convert the Ni simple substance into nickel carbonyl; (3) impregnating nickel carbonyl on the material obtained in the step (2) with an organic solvent; (4) and (4) filtering, drying and roasting the material obtained in the step (3) to obtain the hydrocracking catalyst with the activity recovered. The method enables the Ni poisoned hydrocracking catalyst to recover activity.
Description
Technical Field
The invention relates to a preparation method of a hydrocracking catalyst, in particular to a method for recovering the activity of a Ni-poisoned hydrocracking catalyst.
Background
In recent years, with the progress of crude oil heaviness and deterioration problems and the development of deep vacuum distillation processes, the problem of catalyst metal deposition deactivation due to the metal nickel impurities carried by the hydrocracking feedstock has increased. With respect to the loss of catalyst activity caused by such metal deposition, it is difficult to achieve the restoration of catalyst activity by the conventional carbon-burning method. Chinese patent CN201010222029.6 also discloses a method for regenerating a hydrogenation catalyst, which comprises roasting the catalyst to be regenerated in an oxygen-containing atmosphere to remove carbon deposition, and then sulfurizing the catalyst, wherein the method is only suitable for the deactivation caused by carbon deposition of the catalyst, and is ineffective for the deactivation caused by metal deposition; chinese patent CN201280015492.0 discloses a method for regenerating hydrocracking catalyst, which adopts the mode of burning carbon in air atmosphere to treat spent catalyst, and controls the carbon content of the regenerating agent by adjusting the roasting time and the roasting temperature. This method also fails to address catalyst deactivation caused by catalyst metal deposition.
Disclosure of Invention
In view of the deficiencies of the prior art, the present invention provides a method for preparing a hydrocracking catalyst, which is capable of restoring the activity of a Ni-poisoned hydrocracking catalyst.
A preparation method of a hydrocracking catalyst comprises the following steps:
(1) reducing the to-be-generated hydrocracking catalyst deposited with metal Ni impurities;
(2) carrying out carbonylation treatment on the material subjected to reduction treatment in the step (1) to convert the Ni simple substance into nickel carbonyl;
(3) impregnating nickel carbonyl on the material obtained in the step (2) with an organic solvent;
(4) and (4) filtering, drying and roasting the material obtained in the step (3) to obtain the hydrocracking catalyst with the activity recovered.
In the above method, it is preferable that the method further comprises a step (5), wherein the step (5) is to load the active metal on the hydrocracking catalyst with restored activity obtained in the step (4), and then to dry and calcine the loaded active metal.
In the method, the reduction treatment in the step (1) adopts high-temperature treatment in a hydrogen atmosphere, the pressure is controlled to be 1.0-10.0MPa, the temperature is 400-500 ℃, and the treatment time is 10-50 h.
In the method, the spent catalyst for depositing the metal Ni impurities in the step (1) comprises 1-5% of nickel metal impurities in terms of oxides and 3-20% of carbon in terms of mass percentage, based on the total mass of the spent hydrocracking catalyst, and the balance of components in a conventional hydrocracking catalyst (a fresh agent).
In the method, the spent catalyst for depositing the metal Ni impurity in the step (1) contains 35-70% of a silicon-aluminum carrier containing a Y molecular sieve, 3-20% of carbon and 15-45% of metal oxide (including active metal components of VIII groups and VI groups and Ni impurities) by weight. The VIII-group active metal can be Ni and/or Co, the VI-group active metal can be W and/or Mo, the VIII-group active metal oxide content is generally 3-15%, and the VI-group active metal oxide content is generally 10-40%. Based on the weight of the carrier, the content of the Y molecular sieve in the silicon-aluminum carrier containing the Y molecular sieve is generally 5-90%, preferably 10-70%, and the rest is amorphous silica-aluminum and/or alumina.
In the method, the carbonylation reagent adopted in the carbonylation treatment in the step (2) is one or more of CO, acyl halide or acyl anhydride; preferably CO or a mixture containing CO, which may be CO and N2、O2、CO2And one or more mixtures in air, preferably a mixed gas of CO and air, wherein the concentration of CO in the mixed gas is 10-100 v%.
In the method, the carbonylation treatment in the step (2) is to contact the material subjected to reduction treatment in the step (1) with a carbonylation reagent for carbonylation reaction, and the carbonylation treatment conditions are that the treatment temperature is 40-120 ℃ and the treatment time is 30-100 h.
In the above method, the organic solvent in step (3) is at least one of ethanol, diethyl ether, chloroform, carbon tetrachloride and benzene, preferably ethanol or diethyl ether; the volume ratio of the organic solvent to the catalyst is 5: 1-15: 1, and the dipping time is 5-20 h.
In the method, the drying condition in the step (4) is that the drying temperature is 100-.
In the above method, the method for supporting the active metal in step (5) may adopt any one of the processes of the prior art. For example, impregnation, over-volume impregnation or equal volume impregnation may be used, and impregnation may be performed once or more than once.
In the above method, the active metal in step (5) includes a group vi active metal and/or a group viii active metal, and the group vi active metal may be W and/or Mo; the group VIII active metal may be Ni and/or Co, preferably nickel. The active impregnation loading amount is that the content of the VI group active metal oxide in the final catalyst is 10-40% generally, and the content of the VIII group active metal oxide in the final catalyst is 3-15% generally.
In the method, the drying temperature in the step (5) is 100-150 ℃, the drying time is 2-5h, the roasting is carried out in the air atmosphere, and the roasting is carried out at 400-600 ℃ for 2-20 h.
The invention realizes the regeneration of the deactivated hydrocracking catalyst caused by the deposition of the metallic nickel by converting the nickel deposited on the industrial deactivated hydrocracking catalyst into nickel carbonyl and then removing and recovering the nickel carbonyl by utilizing the characteristic of solubility of the nickel carbonyl in part of organic solvent.
Detailed Description
The action and effect of the method of the present invention will be further described with reference to examples and comparative examples, but the following examples are not intended to limit the method of the present invention, and% are by mass unless otherwise specified.
The catalyst (spent catalyst) used for regeneration in the examples is an industrial operation catalyst sample, and the physicochemical properties of the sample before and after the industrial operation are as follows:
TABLE 1 physicochemical Properties of the catalyst used for regeneration
Example 1
(1) Taking a catalyst sample after industrial operation in the table 1, placing the catalyst sample in a reactor, pressurizing hydrogen to 2.0MPa, then heating to 430 ℃ at a heating rate of 20 ℃/h, and reducing at a constant temperature for 36h (supplementing hydrogen into the system along with the consumption of hydrogen in the reduction process to keep the pressure constant);
(2) adding the sample subjected to hydrogen reduction in the step 1 into a carbonylation reactor, introducing a CO + air mixed gas flow into the reactor (the CO content is 30 v%), and treating the mixture for 30 hours at 80 ℃ under normal pressure;
(3) adding the catalyst sample obtained in the step 2 into an ethanol solvent, and controlling the volume ratio of the catalyst to the ethanol to be 1: 10, dipping for 10 h;
(4) 3, filtering an ethanol solution from the catalyst sample soaked by the ethanol, drying the catalyst sample at 120 ℃ for 3 hours, placing the catalyst sample in a muffle furnace, and roasting the catalyst sample at the constant temperature of 440 ℃ for 2 hours, wherein the carbon content of the roasted catalyst is 0.4wt%, and the NiO content is 0.3 wt%;
(5) preparing a nickel nitrate solution (the content of nickel oxide in the solution is 9.8g/100 ml), and impregnating the catalyst sample subjected to the charcoal burning treatment in the step 4 according to a liquid/solid ratio of 7: 1;
(6) and 5, drying the catalyst impregnated by the nickel nitrate solution at 120 ℃ for 4h, and roasting the catalyst at 500 ℃ for 4h to obtain the final catalyst, which is numbered C-1.
Example 2
(1) Taking a catalyst sample after industrial operation in the table 1, placing the catalyst sample in a reactor, pressurizing hydrogen to 3.5MPa, then heating to 450 ℃ at a heating rate of 20 ℃/h, and reducing at a constant temperature for 25h (supplementing hydrogen into the system along with the consumption of hydrogen in the reduction process to keep the pressure constant);
(2) adding the sample subjected to hydrogen reduction in the step 1 into a carbonylation reactor, introducing a CO + air mixed gas flow into the reactor (the CO content is 40 v%), and treating for 35 hours at 70 ℃ under normal pressure;
(3) adding the catalyst sample obtained in the step 2 into a carbon tetrachloride solvent, and controlling the volume ratio of the catalyst to the carbon tetrachloride to be 1: 8, dipping for 10 h;
(4) 3, filtering a carbon tetrachloride solution from a catalyst sample impregnated with carbon tetrachloride, drying at 150 ℃ for 4 hours, placing in a muffle furnace, roasting at 480 ℃ for 3 hours at constant temperature, wherein the content of carbon on the roasted catalyst is 0.1wt%, and the content of NiO is 0.2 wt%;
(5) preparing a nickel nitrate solution (the content of nickel oxide in the solution is 9.8g/100 ml), and impregnating the catalyst sample subjected to the charcoal burning treatment in the step 4 according to a liquid/solid ratio of 6: 1;
(6) and 5, drying the catalyst impregnated by the nickel nitrate solution at 120 ℃ for 4h, and roasting the catalyst at 500 ℃ for 4h to obtain the final catalyst, which is numbered C-2.
Example 3
(1) Taking a catalyst sample after industrial operation in the table 1, placing the catalyst sample in a reactor, pressurizing hydrogen to 4.0MPa, then heating to 490 ℃ at a heating rate of 20 ℃/h, and carrying out constant-temperature reduction for 13h (supplementing hydrogen into the system along with hydrogen consumption in the reduction process to keep the pressure constant);
(2) adding the sample subjected to hydrogen reduction in the step 1 into a carbonylation reactor, introducing a CO + air mixed gas flow into the reactor (the CO content is 20 v%), and treating for 50 hours at 100 ℃ under normal pressure;
(3) adding the catalyst sample obtained in the step 2 into an ether solvent, and controlling the volume ratio of the catalyst to the ether to be 1: 15, soaking for 10 hours;
(4) filtering ether solution from the catalyst sample obtained in the step 3, drying at 120 ℃ for 4h, placing in a muffle furnace, roasting at 430 ℃ for 4h at constant temperature, wherein the carbon content on the roasted catalyst is 0.5wt%, and the NiO content is 0.25 wt%;
(5) preparing a nickel nitrate solution (the content of nickel oxide in the solution is 9.8g/100 ml), and impregnating the catalyst sample subjected to the charcoal burning treatment in the step 4 according to a liquid/solid ratio of 5: 1;
(6) and 5, drying the catalyst impregnated by the nickel nitrate solution at 120 ℃ for 4h, and roasting the catalyst at 500 ℃ for 4h to obtain the final catalyst, wherein the number of the final catalyst is C-3.
Example 4
(1) Taking a catalyst sample after industrial operation in the table 1, placing the catalyst sample in a reactor, pressurizing hydrogen to 2.5MPa, then heating to 450 ℃ at a heating rate of 20 ℃/h, and reducing at a constant temperature for 28h (supplementing hydrogen into the system along with the consumption of hydrogen in the reduction process to keep the pressure constant);
(2) adding the sample subjected to hydrogen reduction in the step 1 into a carbonylation reactor, introducing a CO + air mixed gas flow into the reactor (the CO content is 20 v%), and treating the mixture for 80 hours at 40 ℃ under normal pressure;
(3) adding the catalyst sample obtained in the step 2 into an ether solvent, and controlling the volume ratio of the catalyst to the ether to be 1: 10, soaking for 15 h;
(4) filtering the catalyst sample obtained in the step 3, drying the ether solution for 4 hours at 120 ℃, placing the dried catalyst sample in a muffle furnace, roasting the catalyst sample for 4 hours at the constant temperature of 450 ℃, wherein the carbon content of the roasted catalyst is 0.3wt%, and the NiO content is 0.3 wt%;
(5) preparing a nickel nitrate solution (the content of nickel oxide in the solution is 9.8g/100 ml), and impregnating the catalyst sample subjected to the charcoal burning treatment in the step 4 according to a liquid/solid ratio of 5: 1;
(6) and 5, drying the catalyst impregnated by the nickel nitrate solution at 120 ℃ for 4h, and roasting the catalyst at 500 ℃ for 4h to obtain the final catalyst, wherein the number of the final catalyst is C-4.
Example 5
(1) Taking a catalyst sample after industrial operation in the table 1, placing the catalyst sample in a reactor, pressurizing hydrogen to 8.0MPa, then heating to 420 ℃ at a heating rate of 20 ℃/h, and carrying out constant-temperature reduction for 18h (supplementing hydrogen into the system along with the consumption of hydrogen in the reduction process to keep the pressure constant);
(2) adding the sample subjected to hydrogen reduction in the step 1 into a carbonylation reactor, introducing a CO + air mixed gas flow into the reactor (the CO content is 50 v%), and treating for 55 hours at 40 ℃ under normal pressure;
(3) adding the catalyst sample obtained in the step 2 into an ethanol solvent, and controlling the volume ratio of the catalyst to the ethanol to be 1: 6, dipping for 18 h;
(4) filtering the ethanol solution of the catalyst sample obtained in the step 3, drying the ethanol solution at 130 ℃ for 4 hours, placing the dried catalyst sample in a muffle furnace, roasting the catalyst sample at the constant temperature of 440 ℃ for 4 hours, wherein the carbon content of the roasted catalyst is 0.5wt%, and the NiO content is 0.22 wt%;
(5) preparing a nickel nitrate solution (the content of nickel oxide in the solution is 9.8g/100 ml), and impregnating the catalyst sample subjected to the charcoal burning treatment in the step 4 according to a liquid/solid ratio of 5: 1;
(6) and 5, drying the catalyst impregnated by the nickel nitrate solution at 120 ℃ for 4h, and roasting the catalyst at 500 ℃ for 4h to obtain the final catalyst, wherein the number of the final catalyst is C-5.
Example 6
(1) Taking a catalyst sample after industrial operation in the table 1, placing the catalyst sample in a reactor, pressurizing hydrogen to 1.5MPa, then heating to 420 ℃ at a heating rate of 20 ℃/h, and reducing at a constant temperature for 60h (supplementing hydrogen into the system along with the consumption of hydrogen in the reduction process to keep the pressure constant);
(2) adding the sample subjected to hydrogen reduction in the step 1 into a carbonylation reactor, introducing a mixed gas flow of CO and CO2 into the reactor (the CO content is 50 v%), and treating for 55 hours at 40 ℃ under normal pressure;
(3) adding the catalyst sample obtained in the step 2 into an ethanol solvent, and controlling the volume ratio of the catalyst to the ethanol to be 1: 6, dipping for 18 h;
(4) filtering the ethanol solution of the catalyst sample obtained in the step 3, drying the ethanol solution at 130 ℃ for 4 hours, placing the dried catalyst sample in a muffle furnace, roasting the catalyst sample at the constant temperature of 500 ℃ for 4 hours, wherein the carbon content of the roasted catalyst is 0.1wt%, and the NiO content is 0.20 wt%;
(5) preparing a nickel nitrate solution (the content of nickel oxide in the solution is 9.8g/100 ml), and impregnating the catalyst sample subjected to the charcoal burning treatment in the step 4 according to a liquid/solid ratio of 5: 1;
(6) and 5, drying the catalyst impregnated by the nickel nitrate solution at 120 ℃ for 4h, and roasting the catalyst at 500 ℃ for 4h to obtain the final catalyst, wherein the number of the final catalyst is C-6.
Example 7
(1) Taking a catalyst sample after industrial operation in the table 1, placing the catalyst sample in a reactor, pressurizing hydrogen to 4.0MPa, then heating to 450 ℃ at a heating rate of 20 ℃/h, and reducing at a constant temperature for 23h (supplementing hydrogen into the system along with the consumption of hydrogen in the reduction process to keep the pressure constant);
(2) adding the sample reduced by the hydrogen in the step 1 into a carbonylation reactor, introducing a mixed gas flow of CO and N2 into the reactor (the CO content is 70 v%), and treating for 80 hours at 40 ℃ under normal pressure;
(3) adding the catalyst sample obtained in the step 2 into a benzene solvent, and controlling the volume ratio of the catalyst to the benzene to be 1: 12, dipping for 10 hours;
(4) 3, filtering the obtained catalyst sample to remove benzene solution, drying at 150 ℃ for 4h, placing the dried catalyst sample in a muffle furnace, roasting at 460 ℃ for 4h at constant temperature, wherein the carbon content on the roasted catalyst is 0.2wt%, and the NiO content is 0.25%;
(5) preparing a nickel nitrate solution (the content of nickel oxide in the solution is 9.8g/100 ml), and impregnating the catalyst sample subjected to the charcoal burning treatment in the step 4 according to a liquid/solid ratio of 5: 1;
(6) and 5, drying the catalyst impregnated by the nickel nitrate solution at 120 ℃ for 4h, and roasting the catalyst at 500 ℃ for 4h to obtain the final catalyst, wherein the number of the final catalyst is C-7.
Comparative example 1
The spent catalyst (see table 1) is regenerated by an industrial conventional regeneration method at the air atmosphere, the roasting temperature of 440 ℃ and the roasting time of 4h to obtain the catalyst of the comparative example, which is numbered BC-1.
Comparative example 2
(1) Taking a catalyst sample after industrial operation in the table 1, placing the catalyst sample in a reactor, pressurizing hydrogen to 2.0MPa, then heating to 450 ℃ at a heating rate of 20 ℃/h, and reducing the catalyst sample at a constant temperature for 30h (in the reduction process, along with the consumption of hydrogen, supplementing hydrogen into the system to keep the pressure constant);
(2) adding the sample subjected to hydrogen reduction in the step 1 into a carbonylation reactor, introducing a CO + air mixed gas flow into the reactor (the CO content is 70 v%), and treating for 70 hours at 50 ℃ under normal pressure;
(3) adding the catalyst sample obtained in the step 2 into an ethanol solvent, and controlling the volume ratio of the catalyst to the ethanol to be 1: 10, dipping for 10 h;
(4) and 3, filtering the ethanol solution of the catalyst sample soaked by the ethanol, drying the catalyst sample at 120 ℃ for 3 hours, placing the catalyst sample in a muffle furnace, roasting the catalyst sample at the constant temperature of 440 ℃ for 4 hours, and obtaining the final catalyst with the carbon content of 0.4wt% and the NiO content of 0.30wt% after roasting, wherein the final catalyst is numbered BC-2.
The results of physical and chemical property analyses of the catalysts of examples 1 to 7 and comparative examples are shown in tables 2 to 4. The results of comparative evaluations of the catalysts of examples 1 to 7 and comparative examples are shown in tables 5 to 8. The comparative evaluation test method comprises the steps of adopting a VGO vacuum wax oil raw material, connecting a single section in series and passing through a flow once, filling an industrial refined catalyst FF-66 in a first reaction, and filling a fresh catalyst, an example catalyst and a comparative example catalyst in a second reaction respectively. The specific data are as follows:
table 2 examples 1-4 regenerated catalyst analysis results
| C-1 | C-2 | C-3 | C-4 | |
| The chemical composition is as follows: m% | ||||
| MoO3 | 20.1 | 20.3 | 20.5 | 20.5 |
| NiO | 6.2 | 6.5 | 6.6 | 6.6 |
| Alumina oxide | 50 | 50 | 50 | 50 |
| Molecular sieves | 23 | 23 | 23 | 23 |
| Physical properties: | ||||
| pore volume, mL/g | 0.28 | 0.29 | 0.28 | 0.28 |
| Specific surface area, m2/g | 338 | 345 | 335 | 342 |
| Carbon content, wt% | 0.4 | 0.1 | 0.5 | 0.2 |
Table 3 analysis results of examples 5 to 7 regenerated catalysts
| C-5 | C-6 | C-7 | |
| The chemical composition is as follows: m% | |||
| MoO3 | 20.5 | 20.3 | 20.5 |
| NiO | 6.5 | 6.4 | 6.5 |
| Alumina oxide | 50 | 50 | 50 |
| Molecular sieves | 23 | 23 | 23 |
| Physical properties: | |||
| pore volume, mL/g | 0.27 | 0.29 | 0.28 |
| Specific surface area, m2/g | 338 | 350 | 336 |
| Carbon content, m% | 0.5 | 0.1 | 0.3 |
TABLE 4 analysis results of physical and chemical properties of regenerated catalysts in comparative examples
| BC-1 | BC-2 | |
| The chemical composition is as follows: m% | ||
| MoO3 | 19.5 | 21.8 |
| NiO | 9.4 | 0.3 |
| Alumina oxide | 49 | 53 |
| Molecular sieves | 22 | 25 |
| Physical properties: | ||
| pore volume, mL/g | 0.28 | 0.31 |
| Specific surface area, m2/g | 338 | 375 |
| Carbon content, m% | 0.4 | 0.4 |
TABLE 5 comparative evaluation of stock oil Properties
| Raw oil | VGO vacuum wax oil |
| Density, g/cm3 | 0.9055 |
| Distillation range, deg.C | 310～510 |
| C，m% | 86.38 |
| H，m% | 12.60 |
| S，m% | 1.25 |
| N，% | 980 |
TABLE 6 evaluation conditions and results of fresh catalyst and regenerated catalyst of comparative example regeneration method
| Fresh agent | Comparative example 1 | Comparative example 2 | |
| Reaction temperature of | 375 | 375 | 375 |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 |
| Cracking volume space velocity, h-1 | 1.5 | 1.5 | 1.5 |
| Volume ratio of hydrogen to oil | 1200 | 1200 | 1200 |
| Refined oil nitrogen content, ppm | 5 | 5 | 5 |
| Per pass conversion at more than 350 ℃ m% | 78.2 | 54.0 | 36.7 |
TABLE 7 evaluation conditions and results of examples 1 to 4
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Reaction temperature of | 375 | 375 | 375 | 375 |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| Cracking volume space velocity, h-1 | 1.5 | 1.5 | 1.5 | 1.5 |
| Volume ratio of hydrogen to oil | 1200 | 1200 | 1200 | 1200 |
| Refined oil nitrogen content, ppm | 5 | 5 | 5 | 5 |
| Per pass conversion at more than 350 ℃ m% | 65.2 | 66.3 | 64.8 | 65.0 |
TABLE 8 evaluation conditions and results of examples 5 to 7
| Example 5 | Example 6 | Example 7 | |
| Reaction temperature of | 375 | 375 | 375 |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 |
| Cracking volume space velocity, h-1 | 1.5 | 1.5 | 1.5 |
| Volume ratio of hydrogen to oil | 1200 | 1200 | 1200 |
| Refined oil nitrogen content, ppm | 5 | 5 | 5 |
| Per pass conversion at more than 350 ℃ m% | 64.0 | 65.2 | 65.5 |
Claims (15)
1. A method for restoring activity of a hydrocracking catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) reducing the to-be-generated hydrocracking catalyst deposited with metal Ni impurities;
(2) carrying out carbonylation treatment on the material subjected to reduction treatment in the step (1) to convert the Ni simple substance into nickel carbonyl;
(3) impregnating nickel carbonyl on the material obtained in the step (2) with an organic solvent;
(4) and (4) filtering, drying and roasting the material obtained in the step (3) to obtain the hydrocracking catalyst with the activity recovered.
2. The method of claim 1, wherein: the method comprises the step (5), wherein the step (5) is to load active metal on the hydrocracking catalyst with recovered activity prepared in the step (4), and then drying and roasting are carried out.
3. The method of claim 1, wherein: the reduction treatment in the step (1) adopts high-temperature treatment in a hydrogen atmosphere, the pressure is controlled to be 1.0-10.0MPa, the temperature is controlled to be 400-500 ℃, and the treatment time is 10-50 h.
4. The method of claim 1, wherein: the spent catalyst for depositing the metal Ni impurities in the step (1) comprises 1-5% of nickel metal impurities and 3-20% of carbon impurities in percentage by mass in terms of oxides based on the total mass of the spent hydrocracking catalyst.
5. The method of claim 1, wherein: the spent catalyst for depositing the metal Ni impurities in the step (1) contains 35-70% of a silicon-aluminum carrier containing a Y molecular sieve, 3-20% of carbon and 15-45% of metal oxide by weight.
6. The method of claim 5, wherein: the metal oxide comprises active metal components of a VIII family and a VI family and Ni impurities, wherein the active metal of the VIII family is Ni and/or Co, the active metal of the VI family is W and/or Mo, the content of the active metal oxide of the VIII family is 3-15%, and the content of the active metal oxide of the VI family is 10-40%.
7. The method of claim 1, wherein: the carbonylation reagent adopted in the carbonylation treatment in the step (2) is one or more of CO, acyl halide or acyl anhydride.
8. The method of claim 7, wherein: the carbonylation reagent adopts CO or a mixed gas containing CO, and the mixed gas containing CO can be CO and N2、O2、CO2And one or a mixture of a plurality of air, wherein the concentration of CO in the mixed gas is 10-100 v%.
9. The method of claim 1, wherein: and (2) the carbonylation treatment is to contact the material subjected to reduction treatment in the step (1) with a carbonylation reagent for carbonylation reaction, wherein the carbonylation treatment conditions are that the treatment temperature is 40-120 ℃ and the treatment time is 30-100 h.
10. The method of claim 1, wherein: the organic solvent in the step (3) is at least one of ethanol, diethyl ether, chloroform, carbon tetrachloride and benzene; the volume ratio of the organic solvent to the catalyst is 5: 1-15: 1, and the dipping time is 5-20 h.
11. The method of claim 1, wherein: and (4) drying at the drying temperature of 100-150 ℃ for 2-5h, roasting at the roasting treatment condition of 400-500 ℃ for 3-10h in an air atmosphere, wherein the carbon content of the hydrocracking catalyst after roasting to restore the activity is 0.2-1 wt%, and the nickel content of the hydrocracking catalyst is less than 0.5wt% in terms of oxide.
12. The method of claim 2, wherein: and (5) adopting an impregnation method, and carrying out over-volume impregnation or equal-volume impregnation.
13. The method of claim 12, wherein: the active metal in the step (5) comprises a VI group active metal and/or a VIII group active metal, and the VI group active metal is W and/or Mo; the group VIII active metal is Ni and/or Co.
14. The method of claim 13, wherein: the active impregnation loading amount is 10-40% of the VI group active metal oxide and 3-15% of the VIII group active metal oxide in the final catalyst.
15. The method of claim 2, wherein: in the step (5), the drying temperature is 100-150 ℃, the drying time is 2-5h, the roasting is carried out in the air atmosphere, and the roasting is carried out at 400-600 ℃ for 2-20 h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198366A (en) * | 1997-05-06 | 1998-11-11 | 中国石油化工总公司 | Dry demetallization regeneration technology for residue and/or heavy oil catalytic cracking catalyst |
| CN1335359A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Method of regenerating hydrogenation cracking catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198366A (en) * | 1997-05-06 | 1998-11-11 | 中国石油化工总公司 | Dry demetallization regeneration technology for residue and/or heavy oil catalytic cracking catalyst |
| CN1335359A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Method of regenerating hydrogenation cracking catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 孙贵范 主编: "《中华医学百科全书 职业卫生与职业医学》", 31 January 2019, 中国协和医科大学出版社 * |
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