CN104588094B - The renovation process of decaying catalyst - Google Patents
The renovation process of decaying catalyst Download PDFInfo
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Abstract
The invention discloses the renovation process of a kind of decaying catalyst.This decaying catalyst includes TON type acidic zeolite component and metal component of group VIII, regenerative process is as follows: first process deactivation catalyst of carbon deposit by organic solution, infusion process is used to load nickel compound containing again, in the addition of nickel and catalyst, the atomic ratio of metal platinum is 6:1 ~ 1:1, after obtain the regenerated catalyst of activation recovering through making charcoal.Compared with prior art, regeneration methods of the invention is not only able to the most effectively remove carbon deposit, and can guarantee that catalyst pore structure is not destroyed, it is to avoid noble metal is assembled, noble metal dispersion is good, so that the reactivity worth of regenerated catalyst can be recovered to fresh catalyst level.The method is particularly suitable for the regeneration of the hydroisomerization dewaxing catalyst of inactivation.
Description
Technical field
The present invention relates to the renovation process of a kind of decaying catalyst.It is more particularly related to a kind of paraffin hydrocarbon is selected
The renovation process of shape isomerization catalyst, is particularly suitable for the catalyst regeneration side that the hydroisomerization dewaxing process of lubricating oil uses
Method.
Background technology
Isodewaxing Technology is mainly used in the hydrogen that faces of diesel oil, wax oil and other specialty oils and processes, to reduce
Normal paraffin content, improves the purpose of oil quality.This technology also has important meaning to the low temperature flow improving diesel oil.One
For as, in straight-run diesel oil or secondary processing diesel oil, wax content is higher, and therefore its condensation point or cold filter plugging point are defective, reduces diesel oil
Productivity, n-alkane can be converted into the isoparaffin of low condensation point by hydroisomerization effectively, and it is high by 16 to retain it
The feature of alkane value.Producing high-quality extraordinary oil as the tail oil being hydrocracked about VGO or modifying, hydroisomerization closes especially
Key technology.By the isomerization of long-chain normal paraffin, the distillate component of low pour point, high viscosity index (HVI), low volatility can be produced,
So exploitation isomerization dewaxing catalyst regeneration techniques not only has good economic benefit, and its social meaning is the most important
With far-reaching.
The catalyst in use activity that oil-refining chemical process uses can be gradually lowered, i.e. catalysqt deactivation, concludes
Reason of getting up be generally divided into coking and deactivation (causing catalyst pores to block), poisoning and deactivation (causing acidity of catalyst center to be poisoned) and
Sintering deactivation (causing the change of catalyst crystalline phases) etc..The main cause of industry hydrogenation catalyst inactivation is that coke generates and metal
Blocking, active metal component migrates or gatherings, the change of phase composition, number of active center reduces, carrier sinters, zeolite structured subsides
With collapse etc..The decaying catalyst caused for carbon deposit can recover its activity by regeneration method, and pollutes for metal deposit
The decaying catalyst caused, it is impossible to regeneration is allowed to activity recovery, can only discard.
Catalyst regeneration is divided into in-situ regeneration and ex-situ regeneration two kinds, and in-situ regeneration typical media is nitrogen and air, to the greatest extent
Amount is without steam and air, because steam can promote accumulation of metal on catalyst, zeolite crystalline structure to be destroyed.Due to
In-situ regeneration shortcoming is too many, seldom uses which to carry out catalyst regeneration.The most industrial, the most large-scale reactor
In catalyst all use ex-situ regeneration technique.The major advantage of catalyst device outer regeneration technology be in catalyst regeneration process not
Being easily generated hot-spot, catalyst activity recovery extent is higher；The natural law that goes into operation of device can be increased；And device reaction system
Without bearing the corrosion of sulfurous gas in regeneration gas again.
The essence of ex-situ regeneration patented technology is contacting by decaying catalyst and oxygen-containing gas, removes the long-pending of surface
Charcoal, i.e. makes catalyst regenerate by the way of making charcoal.Compared with fresh catalyst, the pore volume of regenerated catalyst, specific surface area are all
There is a certain degree of decline, and the fall of activity is the biggest.
In order to improve the activity of regenerated catalyst, patented technology also elaborates certain methods, to urging after regeneration
Agent carries out post processing, proposes to contact catalyst with additive such as CN1187215A and activates, does the most under certain condition
Dry described catalyst so that described additive remains substantially in catalyst, described additive be selected from least two hydroxyl and 2 ~
The compound of 10 carbon atoms and at least one compound of the ether of these compounds.WO01/02092 describe a kind of by with
Under type is by the regeneration of used catalyst based on additive and the method for activation: by this catalysis at maximum temperature is 500 DEG C
Agent contacts with oxygen-containing gas, makes it activate by contacting with organic additive subsequently, then is dried through uniform temperature, to ensure extremely
The described additive of few 50% is maintained in this catalyst.Preferably additive be selected from comprise the oxygen-containing part of at least two and 2 ~
The compound of 10 carbon atoms and the compound derived by these compounds.Mentioned example includes acid, aliphatic diol, fat
Race's glycol ethers, saccharide and oxygenatedchemicals.Method described in CN1890351A is: by catalyst with acid and boiling point be 80 ~ 500 DEG C with
And the dissolubility in water is at least the organic additive contact of 5g/L, it is dried so that the institute of at least 50wt% under certain condition
State additive to retain in the catalyst.Above-mentioned ex-situ regeneration method is owing to make charcoal step through high temperature, the most again with organic
Additive treating, the method is not suitable for noble metal and molecular screen material in the isomerization dewaxing catalyst as active component.
The active metal that isomerization dewaxing catalyst uses is generally noble metal, and carrier typically uses TON molecular sieve, is a kind of
Contain the catalyst of noble metal and molecular sieve simultaneously.This catalyst has suitable acid centre and high hydrogenation activity so that it is
Selective hydrocracking and hydroisomerization function reach well to balance, and so can make the wax isomerization reactivity of catalyst
Being greatly improved with selectivity, be in particular in that yield dewaxed oil and viscosity index (VI) are all improved, pour point is substantially reduced.
Isomerization dewaxing catalyst main cause of activity decrease in hydroisomerization dewaxing reacts include following some: (1)
On catalyst, carbon deposit covers the active sites of catalyst or plugs the duct of catalyst；(2) chemical combination such as sulfur nitrogen in raw material
Thing makes catalyst poisoning；(3) gathering of metal or the destruction of carrier structure；(4) metal or nonmetallic deposition in raw material,
Such as silicon, arsenic, ferrum etc..Owing to isomerization dewaxing catalyst is a kind of macromolecule sieve content noble metal catalyst, molecular sieve is a kind of
Metastable state crystallizes, and (such as high temperature, illumination, long-time etc.) can be converted into more stable structure (generally under certain condition
ZSM-5 molecular sieve structure), the reactivity worth of original catalyst can be lost, at high temperature easily lead to crystallization of molecular sieves structure
Destruction, and be easily caused the gathering of metal, once accumulation of metal, it is impossible to as reforming catalyst, carry out the chlorine of metal
Change and update (at high temperature, chlorine and steam are very big to the destruction of molecular sieve structure), even if using organic additive etc. after making charcoal
Conventional method processes, it is also difficult to make it be disperseed the most well.As can be seen here, conventional catalyst high temperature coke-burning regeneration method
Will the performance of this isomerization dewaxing catalyst of heavy damage.So general noble metal catalyst (such as reforming catalyst) regeneration
Method is not suitable for the regeneration of isomerization dewaxing catalyst, in whole regenerative process, it is necessary to strict control catalyst particle surface
Temperature is too high, and ensures oxidation thoroughly, specially requires the strict regeneration temperature and oxygen-containing of controlling in catalyst regeneration process for this
Amount.So isomerization dewaxing catalyst regeneration it is critical only that and finds a carbon deposit can tried one's best on Removal of catalyst, again can simultaneously
Suppress molecular sieve to be destroyed and reduces the operating condition of accumulation of metal.
In existing relevant deactivation catalyst of carbon deposit Recycling Patents, most of patents consider how emphatically to prevent inactivation from urging
Agent is concentrated or the problem of excessive exotherms in regenerative process.Such as US5,037,785 suggestion, under oxygen containing gas, uses laser
Catalyst is devoked by the method irradiated, US4, and 202,865 suggestion batch (-type)s note oxygen, US4, and 780,195 and US4,417,975 etc.
Then think and in atmosphere, add a certain amount of water to prevent sintering of catalyst etc..CN1768956A thinks that the carbon deposit on catalyst can
To process to obtain more preferable result by distinct methods, be conducive to controlling temperature during its regeneration, reduce high temperature to catalyst
The impact of performance, improves the activity of regenerated catalyst.Its processing mode is to be initially charged carbon deposit cleaner such as propylene glycol monomethyl ether acetic acid
The organic solvents such as ester, propylene-glycol ethyl ether, dipropylene glycol methyl ether, propylene glycol monomethyl ether carry out washing by soaking to decaying catalyst.But
The method solvent load is excessive, and the macromole by-product in detergent is also difficult to separate.And the method is first removed with organic solvent
Remove the carbon deposit that part easily removes, to reduce the liberated heat when coke-burning regeneration, but finally remain a need for high temperature coke combustion, still
So exist the problem that isomerization dewaxing catalyst runs into when high temperature regeneration, particularly metal platinum assemble, molecular sieve structure quilt
The problems such as destruction.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides the renovation process of a kind of decaying catalyst, especially
It is applicable to the renovation process of the shape-selective isomerization dewaxing catalyst of paraffin hydrocarbon.De-carbon can not only be had certain effect by the method, also
Can be prevented effectively from the gathering of noble metal, noble metal dispersion is good, and the performance of regenerated catalyst can be recovered to fresh catalyst level.
The renovation process of decaying catalyst of the present invention, this catalyst includes TON type molecular sieve and the VIIIth race's noble metal component,
Regenerative process includes: decaying catalyst first processes with organic solvent, uses infusion process load to contain after treatment on catalyst
Nickel compound, then under oxygen-containing gas effect, carries out program control making charcoal and obtains regenerated catalyst, the maximum temperature of coke combustion
Less than 450 DEG C.
TON type molecular sieve involved by the method for the present invention can be ZSM-22, SSZ-32, Nu-10, KZ-2 and ISI-1
In one or more, preferably comprise ZSM-22 molecular sieve, noble metal component be selected from group VIII metal platinum.Refractory can also be contained
One or more in porous inorganic oxide, such as aluminium oxide, silicon oxide, titanium oxide, zirconium oxide etc..Weight with catalyst
On the basis of, the content of TON type molecular sieve is 10wt% ~ 90wt%, preferably 30wt% ~ 80wt%, the content of noble metal is 0.05% ~
5.0%, refractory porous inorganic oxide is surplus.
In the inventive method, decaying catalyst first processes with organic solvent, and organic solvent wherein used can be general
Can use one or more in benzene, ethanol, gasoline, kerosene, organic solvent processes the method for decaying catalyst can use leaching
The method that bubble, distillation etc. are conventional.
In the inventive method, use infusion process load nickel compound containing.Impregnation liquid used by infusion process uses nickeliferous chemical combination
Thing aqueous solution is soluble in water formulated, and nickel compound containing aqueous solution can be the soluble nickel such as nickel nitrate, nickel acetate, nickel sulfate
One or more in salt, its concentration is that 1 ~ 10%(is in terms of nickel element), the wherein load capacity of nickel and platinum former in decaying catalyst
Son ratio is 6:1 ~ 1:1, preferably 4:1 ~ 2:1.
In the inventive method, carrying out program control making charcoal under oxygen-containing gas effect, the maximum temperature of coke combustion is less than 450
DEG C, preferably shorter than 420 DEG C.Present invention preferably employs two-stage regeneration: first paragraph is cold stage, second segment is hot stage.The
In one section, temperature 150 DEG C ~ 280 DEG C, described catalyst is contacted with carrier of oxygen, during contact under the conditions of preferably 190 DEG C ~ 280 DEG C
Between be 2h ~ 16h, preferably 4h ~ 12h.In second segment, temperature 300 DEG C ~ 450 DEG C, by institute under the conditions of preferably 320 DEG C ~ 420 DEG C
Stating catalyst to contact with oxygen-containing gas, time of contact is 2h ~ 14h, preferably 3h ~ 8h.In oxygen-containing gas, oxygen content is generally
0.2v% ~ 15v%, preferably 0.5v% ~ 10v%.
The inventive method has the advantage that
(1) first with organic solvent, decaying catalyst is processed, it is possible to decrease the carbon deposit content on decaying catalyst, favorably
Temperature in time controlling its regeneration, when preventing from regenerating, heat release too much or is excessively concentrated, it is to avoid the mistake thermal response of catalyst, causes urging
Agent character changes, and the structure such as molecular sieve is destroyed, or the character of catalyst is caused negative by the enrichment of carried metal
Face rings.
(2) strict control regeneration temperature and oxygen content in program control coke combustion, this is higher owing to containing in catalyst
The TON type molecular sieve of ratio, due to the particularity (being easily converted to the ZSM-5 molecular sieve that structure is more stable) of its molecular sieve, burns
Charcoal temperature is too high, has a strong impact on the degree of crystallinity of molecular sieve, and research display charcoal temperature does not has in the structure of the procatalyst of 450 DEG C
Significant change, but when charcoal temperature 450 DEG C, the structure of catalyst there occurs significantly change, compared with fresh catalyst, phase
It is the XRD figure of fresh dose that degree of crystallinity drops to 97%(Fig. 1), thus oxidation burning process in, charcoal temperature be one important
Factor.When charcoal temperature is relatively low, carbon deposit elimination factor is relatively low, but along with the rising of charcoal temperature, can cause the poly-of active metal
Collection the structure of saboteur's sieve, make the performance of catalyst be a greater impact.In whole regenerative process, it is necessary to strictly control
The temperature of catalyst particle surface is too high, and ensures oxidation thoroughly, but owing to, during making charcoal, the carbon on catalyst exists
Also heat is released, so considering for guaranteeing that catalyst is not burned control temperature at 450 DEG C during burning.
(3) on program control procatalyst of making charcoal, load a certain amount of nickel compound containing, and enter under relatively low regeneration temperature
Row coke-burning regeneration.Owing to nickel can reduce acid strength with the acid centre effect of catalyst, thus reduce the work of carrier and carbon deposit
With, cause carbon deposit to be easier to oxidized and remove, be so not only able to effectively remove carbon deposit, and nickel energy in coke combustion
Effectively avoid the gathering of noble metal, improve the dispersion of noble metal platinum, avoid the destruction of TON type molecular sieve structure simultaneously, carry
The hydrogenation/dehydrogenation reactivity of high catalyst, makes the performance recovery of catalyst to fresh catalyst level.
Accompanying drawing explanation
Fig. 1 is the XRD spectra (100%) of fresh dose of FD-1；
The XRD spectra (99%) of Fig. 2 deactivator FD-1；
The XRD spectra (99%) of Fig. 3 R-420；
The XRD spectra (97%) of Fig. 4 R-450；
The XRD spectra (92%) of Fig. 5 R-500；
Wherein, the R-in Fig. 3-5 refers to that the sintering temperature of catalyst, such as R-420 represent that deactivator is at 420 DEG C of roastings
After reason.Digitized representation relative crystallinity in Fig. 1-Fig. 5 bracket.
Detailed description of the invention
The preparation process of catalyst of the present invention is further illustrated below by embodiment, but it is not considered that the present invention only office
It is limited in below example.In the present invention, wt% is mass fraction.
Regenerated catalyst of the present invention is to use the medium-sized fixed bed reactors of 200ml to be evaluated, and loaded catalyst is
200ml, carries out prereduction to catalyst before charging, makes the noble metal on catalyst be changed into reduction-state, and reducing condition is as follows:
In the presence of hydrogen, temperature 300 DEG C ~ 500 DEG C, pressure 0.5MPa ~ 10MPa, 1 hour ~ 12 hours time, evaluates the raw material used
Oil main character is shown in Table 1.
Table 1 raw oil main character
| Density (20 DEG C), kg/m3 | 861.1 |
| Sulfur, μ g/g | 4.0 |
| Nitrogen, μ g/g | 1.2 |
| Viscosity (40 DEG C), mm/s2 | 29.69 |
| Pour point, DEG C | 21 |
| Wax content, wt% | 9.8 |
| Boiling range, DEG C (D1160) | |
| IBP/10% | 227/399 |
| 30%/50%- | 428/441 |
| 70%/90% | 455/469 |
| 95%/EBP | 477/500 |
The decaying catalyst that the present invention relates to is that fresh catalyst is different at Sinopec Qilu Petrochemical hydrocracking tail oil
As a example by deactivator (FD-1) after structure dewaxing device industrial operation.The physico-chemical property of decaying catalyst is as follows: specific surface area is
103m2/ g, pore volume is 0.28ml/g, Pt content 0.45wt%, and C content is 7.24 wt %.Composition that FD-1 is fresh dose and character
As follows: specific surface area is 235m2/ g, pore volume is 0.35ml/g, Pt content 0.50wt%.
Embodiment 1
The preparation of catalyst E-1 of the present invention.
1450ml organic solution (wherein ethanol and benzene volume volume ratio are 2:1) is added, to work in the flask of 2000ml
200ml hydrogenation tail oil isomerization dewaxing Pt/ZSM-22 decaying catalyst (FD-1, carbon content is 7.24wt%) after industry operating is carried out
Process, the numbered Ea-1 of catalyst after distilling 2 hours.
Take Ca-1 catalyst 100g, add in 15g nickel nitrate (nickel content 3.0wt%) solution and impregnate, prepare the former of Ni with Pt
Son than being the nickeliferous sample of 3:1, then the programming rate with 3 DEG C/min, be warming up to 250 DEG C of constant temperature 10h, then proceed to 3 DEG C/
The programming rate of min, is warming up to 410 DEG C of constant temperature 3h, obtains catalyst E-1 of the present invention, and its physico-chemical property is shown in Table 2, and reaction result is shown in
Table 3.
Embodiment 2
The preparation of catalyst E-2 of the present invention
Take Ea-1 catalyst 100g, add in 10g nickel acetate (nickel content 8.0wt%) solution and impregnate, prepare nickeliferous sample
Product, wherein Ni is 5:1 in the atomic ratio of Pt, then the programming rate with 3 DEG C/min is warming up to 240 DEG C of constant temperature 10h, then proceedes to
With the programming rate of 3 DEG C/min, it is warming up to 420 DEG C of constant temperature 3h, the numbered Eb-1 of gained catalyst.Its physico-chemical property is shown in Table 2, knot
Fruit is shown in Table 3
Embodiment 3
The preparation of catalyst E-3 of the present invention
1450ml organic solvent (wherein gasoline and kerosene volume ratio are 1:1) is added, to industry in the flask of 2000ml
Decaying catalyst FD-1 process after operating, the numbered Cb-1 of catalyst after distilling 2 hours.
Take Cb-1 catalyst 120g, add in 50g nickel sulfate (Ni content 2.0wt%) solution and impregnate, prepare nickeliferous sample
Product, wherein Ni is 6:1 in the atomic ratio of Pt, then the programming rate with 3 DEG C/min is warming up to 280 DEG C of constant temperature 8h, then proceed to
The programming rate of 3 DEG C/min, is warming up to 350 DEG C of constant temperature 5h, obtains catalyst E-3 of the present invention.Its physico-chemical property is shown in Table 3, reaction knot
Fruit is shown in Table 4.
Embodiment 4～6
The preparation of catalyst E-4 ~ E-6 of the present invention
The preparation process of catalyst E-4 ~ E-6 of the present invention with embodiment 1, difference be with molecular sieve used and
Nickel solution is different, the catalyst E-4 ~ E-6 of the present invention prepared, and its concrete treatment conditions are shown in Table 2, and physico-chemical property is shown in Table 3, reaction
The results are shown in Table 4.
Comparative example 1
Prepared by comparative catalyst C-1 of the present invention.
The preparation method of catalyst is with embodiment 1, and difference is that catalyst is without nickel solution processing procedure, numbering
For C-1, its physico-chemical property is shown in Table 3, and reaction result is shown in Table 4.
Comparative example 2
Prepared by comparative catalyst C-2 of the present invention.
The preparation method of catalyst with embodiment 1, though difference be catalyst through nickel solution processing procedure, without
Program control coke combustion, numbered C-2, its physico-chemical property is shown in Table 3, and reaction result is shown in Table 4.
The each embodiment of table 2 and the treatment conditions of comparative example
Note: 1. ethanol/benzene, 2. gasoline/kerosene, 3. Nu-10 molecular sieve, 4. SSZ-32 molecular sieve
The physico-chemical property of table 3 regenerated catalyst
| Numbering | Pore volume, ml/g | Specific surface area, m2/g | C, wt% |
| Fresh dose of FD-1 | 0.35 | 235 | -- |
| Deactivator | 0.28 | 103 | 7.24 |
| E-1 | 0.31 | 228 | 0.10 |
| E-2 | 0.29 | 230 | 0.12 |
| E-3 | 0.33 | 231 | 0.13 |
| E-4 | 0.30 | 229 | 0.8 |
| E-5 | 0.29 | 230 | 0.11 |
| E-6 | 0.30 | 231 | 0.14 |
| C-1 | 0.22 | 185 | 2.80 |
| C-2 | 0.30 | 165 | 1.63 |
Table 4 evaluating catalyst condition and result
Table 4 continues evaluating catalyst condition and result
The evaluation result of table 4 shows, compared with comparative catalyst, uses the catalyst of the inventive method regeneration, is used for moistening
In the hydroprocessing processes of lubricant oil fraction, when lube base oil pour point is close, C5 +Liquid is received and is improved more than 5wt%, lubricates oil base
Plinth oil yield improves more than 10wt%, and the viscosity index (VI) of product improves nearly 11 units, and the catalysis after the inventive method regeneration is described
Agent is processing during crude lube stock, and effect has and significantly improves.
From Fig. 1 to Fig. 5, the degree of crystallinity of fresh dose is set to 100%, and its XDR structure is shown in Fig. 1, and the structure of deactivator is shown in figure
2, the XRD characterization result of the sample that different charcoal temperatures (420 DEG C, 450 DEG C and 500 DEG C) obtain is shown in Fig. 3 ~ Fig. 5, from the knot of Fig. 3
Really it can be seen that there is no significant change at charcoal temperature in the structure of the procatalyst of 420 DEG C, but when charcoal temperature 450 DEG C,
The structure of catalyst there occurs that some change, and when charcoal temperature reaches 500 DEG C, the structure of catalyst there occurs significantly change
Change.
Claims (13)
1. a renovation process for decaying catalyst, this catalyst includes TON type molecular sieve and the VIIIth race's noble metal component, wherein
Noble metal component is platinum, and regenerative process includes:
Decaying catalyst first processes with organic solvent, uses infusion process load nickel compound containing after treatment on catalyst,
Wherein on catalyst, the atomic ratio of the nickel in the nickel compound containing of load and platinum is 6:1 ~ 1:1, then under oxygen-containing gas effect,
Carrying out program control making charcoal, the maximum temperature of coke combustion is less than 450 DEG C.
The most in accordance with the method for claim 1, it is characterised in that: in described catalyst, TON type molecular sieve be ZSM-22,
One or more in Nu-10, KZ-2 and ISI-1.
3. according to the method described in claim 1 or 2, it is characterised in that: in described catalyst, containing TON type molecular sieve, expensive
Metal platinum and refractory porous inorganic oxide, on the basis of the weight of catalyst, the content of molecular sieve is 10wt% ~ 90wt%, expensive
The content of metal is 0.05 wt% ~ 5.0 wt%, and surplus is refractory porous inorganic oxide.
4. according to the method described in claim 1 or 2, it is characterised in that: in described catalyst, containing TON type molecular sieve, expensive
Metal platinum and refractory porous inorganic oxide, on the basis of the weight of catalyst, the content of molecular sieve is 30wt% ~ 80wt%, expensive
The content of metal platinum is 0.05 wt% ~ 5.0 wt%, and surplus is refractory porous inorganic oxide.
5. according to the method described in claim 1 or 2, it is characterised in that: described catalyst is hydroisomerization dewaxing catalyst.
6. according to the method described in claim 1 or 2, it is characterised in that: on catalyst load nickel compound containing in nickel with
In decaying catalyst, the atomic ratio of platinum is 4:1 ~ 2:1.
7. according to the method described in claim 1 or 2, it is characterised in that: decaying catalyst first processes with organic solvent, its
One or more in ethanol, benzene, gasoline and kerosene of organic solvent used by.
8. according to the method described in claim 1 or 2, it is characterised in that: decaying catalyst first processes with organic solvent, its
Middle organic solvent processes the method for decaying catalyst and uses the method soaked or distill.
9. according to the method described in claim 1 or 2, it is characterised in that: organic solvent is 5 with the volume ratio of decaying catalyst:
1。
10. according to the method described in claim 1 or 2, it is characterised in that: use infusion process load nickel compound containing, infusion process
Impregnation liquid used uses nickel compound containing soluble in water formulated, and its concentration is calculated as 1% ~ 10% with nickel element, wherein nickel
Compound is one or more in nickel nitrate, nickel acetate, nickel sulfate.
11. according to the method described in claim 1 or 2, it is characterised in that: program control employing two-stage regeneration, the wherein first paragraph of making charcoal
In, under the conditions of temperature 150 DEG C ~ 280 DEG C, described catalyst being contacted with oxygen-containing gas, time of contact is 2h ~ 16h, second segment
In, under the conditions of temperature 300 DEG C ~ 450 DEG C, described catalyst being contacted with oxygen-containing gas, time of contact is 2h ~ 14h.
12. according to the method described in claim 1 or 2, it is characterised in that: program control employing two-stage regeneration, the wherein first paragraph of making charcoal
In, under the conditions of temperature 190 DEG C ~ 280 DEG C, described catalyst being contacted with oxygen-containing gas, time of contact is 4h ~ 12h, second segment
In, under the conditions of temperature 320 DEG C ~ 420 DEG C, described catalyst being contacted with oxygen-containing gas, time of contact is 3h ~ 8h.
13. according to the method described in claim 1 or 2, it is characterised in that: in oxygen-containing gas, oxygen content is 0.2v% ~ 15v%.
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| CN107199054B (en) * | 2016-03-18 | 2019-09-17 | 中国石油化工股份有限公司 | A kind of metal catalyst recovery method |
| CN106378209A (en) * | 2016-10-13 | 2017-02-08 | 中海油天津化工研究设计院有限公司 | Method for regenerating fats and oils hydrogenation deactivated catalyst |
| CN109701637B (en) * | 2017-10-26 | 2021-08-03 | 中国石油化工股份有限公司 | Regeneration method of toluene methanol side chain alkylation catalyst |
| CN111097514B (en) * | 2018-10-29 | 2022-03-08 | 中国石油化工股份有限公司 | Method for restoring activity of low-activity hydrogenation modified pour point depressing catalyst |
| CN114870911A (en) * | 2022-03-04 | 2022-08-09 | 中化蓝天集团有限公司 | Regeneration method of carbon-supported metal catalyst |
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| CN1093734A (en) * | 1993-04-15 | 1994-10-19 | 中国石油化工总公司石油化工科学研究院 | Method for preparation of catalyst cracking combustion-supporting agent |
| CN1187215A (en) * | 1995-06-08 | 1998-07-08 | 住友金属矿山株式会社 | Hydrotreating catalyst composition, preparation and use thereof |
| CN1890351A (en) * | 2003-10-03 | 2007-01-03 | 阿尔伯麦尔荷兰有限公司 | Process for activating a hydrotreating catalyst |
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