CN106179489B - The regeneration method of decaying catalyst - Google Patents
The regeneration method of decaying catalyst Download PDFInfo
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- CN106179489B CN106179489B CN201510210505.5A CN201510210505A CN106179489B CN 106179489 B CN106179489 B CN 106179489B CN 201510210505 A CN201510210505 A CN 201510210505A CN 106179489 B CN106179489 B CN 106179489B
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Abstract
The invention discloses a kind of regeneration methods of decaying catalyst.The catalyst includes TON types molecular sieve and the VIIIth race's noble metal component, regenerative process are as follows：Decaying catalyst first is handled with organic solvent, nickel-loaded on catalyst after treatment, the atomic ratio of nickel and platinum is 6:1~1:1, then under oxygen-containing gas effect, carry out it is program-controlled makes charcoal, the maximum temperature of coke combustion, will treated catalyst reduction treatment under an atmosphere of hydrogen not higher than 450 DEG C；Then it is middle in vacuum environment or inert atmosphere to be impregnated through the dilute acid soln containing chitosan, it is finally dried and roasts to obtain the catalyst of activation recovering.The method of the present invention is not only able to, at low temperature effectively except carbon deposition removal, ensure that catalyst pore structure is not destroyed, and noble metal dispersion can be made good, the performance of regenerated catalyst is restored very well.
Description
Technical field
The present invention relates to a kind of regeneration methods of decaying catalyst, contain noble metal and TON types more specifically to one kind
The regeneration method of the regeneration method of the catalyst for hydroisomerizing of molecular sieve, especially paraffin hydrocarbon catalyst for hydroisomerizing, it is special
It is not suitable for the catalyst recovery process that the hydroisomerization dewaxing process of lubricating oil uses.
Background technology
The hydrogen that faces that Isodewaxing Technology is mainly used in diesel oil, wax oil and other specialty oils is handled, and is reduced with reaching
Normal paraffin content improves the purpose of oil quality.The technology also has important meaning to the low temperature flow for improving diesel oil.One
As for, wax content is higher in straight-run diesel oil or secondary processing diesel oil, therefore its condensation point or cold filter plugging point are unqualified, reduce diesel oil
Yield, n-alkane can be effectively converted into the isoparaffin of low condensation point by hydroisomerization, and it is high by 16 to retain its
The characteristics of alkane value.The special type oil of high quality is produced as the tail oil for being hydrocracked or modifying about VGO, hydroisomerization is even more to close
Key technology.By the isomerization of long-chain normal paraffin, the fraction oil ingredient of low pour point, high viscosity index (HVI), low volatility can be produced,
So exploitation isomerization dewaxing catalyst regeneration techniques are not only with good economic efficiency, but also its social effect is quite important
With it is far-reaching.
Activity can continuously decrease the catalyst that oil-refining chemical process uses in use, i.e. catalyst inactivation, conclude
Reason of getting up is generally divided into coking and deactivation（Catalyst pores is caused to block）, poisoning and deactivation（Acidity of catalyst center is caused to be poisoned）With
Sintering deactivation（Cause the change of catalyst crystalline phases）Deng.The main reason for industrial hydrogenation catalyst inactivation is coke generation and metal
It blocks, active metal component migration or aggregation, the variation of phase composition, number of active center is reduced, carrier is sintered, zeolite structured collapses
With collapse etc..The decaying catalyst for caused by carbon deposit can restore its activity with regeneration method, and metal deposit is polluted
Caused by decaying catalyst, it is impossible to regeneration be allowed to activity recovery, can only discard.
Catalyst regeneration is divided into two kinds of in-situ regeneration and ex-situ regeneration, and in-situ regeneration typical media is nitrogen and air, is use up
Amount does not have to vapor and air, because vapor can promote accumulation of metal on catalyst, zeolite crystalline structure to be destroyed.Due to
In-situ regeneration shortcoming is too many, seldom carries out catalyst regeneration using which.It is industrial at present, particularly 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
Hot-spot is also easy to produce, catalyst activity recovery extent is higher；The number of days that goes into operation of device can be increased；And device reaction system
Without the corrosion for bearing sulfurous gas in regeneration gas again.
The essence of ex-situ regeneration patented technology is the contact with oxygen-containing gas by decaying catalyst, removes the product on surface
Charcoal makes catalyst regeneration by way of making charcoal.Compared with fresh catalyst, the Kong Rong of regenerated catalyst, specific surface have
A degree of decline, and the fall of activity is also larger.
In order to improve the activity of regenerated catalyst, certain methods are also elaborated in patented technology, to urging after regeneration
Agent is post-processed, and as CN1187215A propositions contact catalyst with additive and is activated, and is done under certain condition later
The dry catalyst so that the additive is remained substantially in catalyst, the additive be selected from least two hydroxyls and 2 ~
At least one compound of the compound of 10 carbon atoms and the ether of these compounds.WO01/02092 describe it is a kind of by with
Under type by the used catalyst regeneration based on additive and activation method：This is catalyzed at being 500 DEG C in maximum temperature
Agent is contacted with oxygen-containing gas, is then made its activation by being contacted with organic additive, is dried using certain temperature, to ensure extremely
Few 50% additive is maintained in the catalyst.Preferred additive be selected from comprising at least two oxygen-containing parts and 2 ~
The compound and the compound as derived from these compounds of 10 carbon atoms.Mentioned example includes acid, aliphatic diol, fat
Race's glycol ethers, carbohydrate and oxygenatedchemicals.CN1890351A the methods are：By catalyst with acid and boiling point be 80 ~ 500 DEG C with
And solubility in water is at least the organic additive contact of 5g/L, dries under certain condition so that the institute of at least 50wt%
Additive is stated to retain in the catalyst.Above-mentioned ex-situ regeneration method is since high temperature to be passed through is made charcoal step, then again with organic
Additive treating, this method are not suitable for using noble metal and molecular screen material as in the isomerization dewaxing catalyst of active component.
The active metal that isomerization dewaxing catalyst uses is generally noble metal, and carrier is generally a kind of using TON molecular sieves
Catalyst containing noble metal and molecular sieve simultaneously.The catalyst has suitable acid centre and high hydrogenation activity, makes it
Selective hydrocracking and hydroisomerization function reach good balance, can make the wax isomerization reactivity of catalyst in this way
It is greatly improved with selectivity, is in particular in that yield dewaxed oil and viscosity index (VI) are improved, pour point is substantially reduced.
Isomerization dewaxing catalyst includes the following the main reason for activity declines in hydroisomerization dewaxing reaction：（1）
Carbon deposit covers the active sites of catalyst or plugs the duct of catalyst on catalyst；（2）The chemical combination such as sulphur, nitrogen in raw material
Object makes catalyst poisoning；（3）The aggregation of metal or the destruction of carrier structure；（4）Metal or nonmetallic deposition in raw material,
Such as silicon, arsenic, iron etc..Since isomerization dewaxing catalyst is a kind of macromolecule sieve content noble metal catalyst, molecular sieve is a kind of
Metastable state crystallizes, under certain condition（Such as high temperature, illumination, long-time etc.）More stable structure can be converted into（Generally
ZSM-5 molecular sieve structure）, the reactivity worth of original catalyst can be lost, easilys lead to crystallization of molecular sieves structure at high temperature
Destruction, and be easy to cause the aggregation of metal, once accumulation of metal, it is impossible into the chlorine of row metal as reforming catalyst
Change update（At high temperature, chlorine and vapor are very big to the destruction of molecular sieve structure）Even if using organic additive etc. after making charcoal
Conventional method processing, it is also difficult to it be made to be disperseed well again.It can be seen that conventional catalyst high temperature coke-burning regeneration method
The performance of the isomerization dewaxing catalyst will seriously be destroyed.So general noble metal catalyst（Such as reforming catalyst）Regeneration
Method is not suitable for the regeneration of isomerization dewaxing catalyst, in entire regenerative process, it is necessary to stringent control catalyst particle surface
Temperature is excessively high, and ensures that oxidation is thorough, specially requires regeneration temperature and oxygen-containing is strictly controlled in catalyst regeneration process thus
Amount.So isomerization dewaxing catalyst regeneration key is to find a carbon deposit that can be as possible on Removal of catalyst, while again can
Inhibit to molecular sieve destruction and reduce the operating condition of accumulation of metal.
In existing related deactivation catalyst of carbon deposit Recycling Patents, most of patents consider how to prevent inactivation from urging emphatically
Agent is concentrated in regenerative process or the problem of excessive exotherms.If US5,037,785 suggests under oxygen containing gas, using laser
The method of irradiation devokes catalyst, US4,202, the 865 intermittent note oxygen of suggestion, US4,780,195 and US4, and 417,975 etc.
Then think to add a certain amount of water in atmosphere to prevent sintering of catalyst etc..CN1768956A thinks that the carbon deposit on catalyst can
It is obtained preferably with being handled by distinct methods as a result, temperature when being conducive to control its regeneration, reduces high temperature to catalyst
The influence of performance improves the activity of regenerated catalyst.Its processing mode is first to add in 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
This method solvent dosage is excessive, and the macromolecular by-product in detergent is also difficult to detach.And this method is first removed with organic solvent
The carbon deposit that easily removes of part is removed, to reduce the heat released in coke-burning regeneration, but finally there is still a need for high temperature coke combustion, still
So there are problems that isomerization dewaxing catalyst is encountered in high temperature regeneration, particularly aggregation, molecular sieve structure quilt occur for metal platinum
The problems such as destruction.
Invention content
In order to overcome shortcoming of the prior art, the present invention provides a kind of regeneration method of decaying catalyst, especially
It is suitable for the molecular sieves of type containing TON and the catalyst recovery process of the VIIIth race's noble metal component, particularly paraffin hydrocarbon hydro-isomerization
The regeneration method of dewaxing catalyst.Using regeneration method of the present invention, carbon deposit is not only removed effectively, and can guarantee catalyst pores
Road is not destroyed, and effectively avoids the aggregation of noble metal, and noble metal dispersion is good, and the performance of regenerated catalyst can be restored to fresh to urge
Agent is horizontal.
The regeneration method of decaying catalyst of the present invention, the catalyst include TON types molecular sieve and the VIIIth race's noble metal component,
Regenerative process includes：Decaying catalyst is first handled with organic solvent, is contained on catalyst using infusion process load after treatment
Nickel and pt atom ratio in the nickel compound containing loaded on nickel compound, wherein catalyst are 6:1~1:1, then in oxygen-containing gas
Under effect, progress is program-controlled to make charcoal, and the maximum temperature of coke combustion is not higher than 450 DEG C；Will treated catalyst in atmosphere of hydrogen
Lower reduction treatment；Then it impregnates through the dilute acid soln containing chitosan under vacuum environment or inert atmosphere, is finally dried
And calcination process, obtain the catalyst of activation recovering.
TON type molecular sieves in catalyst of the present invention, can be in ZSM-22, SSZ-32, Nu-10, KZ-2 and ISI-1
One or more, preferably comprise ZSM-22 molecular sieves, and noble metal is selected from group VIII metal platinum.Refractory porous, inorganic can also be contained
It is one or more in oxide, such as aluminium oxide, silica, titanium oxide, zirconium oxide etc..On the basis of the weight of catalyst,
The content of molecular sieve is 10wt% ~ 90wt%, and preferably 30wt% ~ 80wt%, the content of noble metal is 0.05wt% ~ 5.0wt%, and refractory is more
The content of mesoporous inorganic oxide is surplus.
In the method for the present invention, decaying catalyst is first handled with organic solvent, used in organic solvent generally may be used
Using one or more of benzene, ethyl alcohol, gasoline, kerosene, organic solvent processing decaying catalyst method may be used immersion,
The common methods such as distillation.The volume ratio of organic solvent and catalyst can be 8:1~1:1.
In the method for the present invention, infusion process load nickel compound containing may be used.Maceration extract used in infusion process is using nickeliferous
The aqueous solution of compound, the aqueous solution of nickel compound can be the soluble nickel salts such as nickel nitrate, nickel acetate, nickel chloride, nickel sulfate
In it is one or more, the concentration of aqueous solution of nickel compound is 1.0 wt% ~ 10.0wt%（In terms of nickel element）, the wherein load of nickel
The atomic ratio of amount and platinum in decaying catalyst is 6:1~1:1, preferably 6:1~2:1, further preferably 4:1~2:1.
In the method for the present invention, carried out under oxygen-containing gas effect it is program-controlled make charcoal, the maximum temperature of coke combustion is not higher than 450
DEG C, preferably no greater than 420 DEG C.Present invention preferably employs two sections to make charcoal：First segment is made charcoal the stage for low temperature, and second segment is burnt for high temperature
The charcoal stage.In first segment, the catalyst is connect with carrier of oxygen under the conditions of 150 DEG C ~ 280 DEG C, preferably 190 DEG C ~ 280 DEG C of temperature
It touches, time of contact is 2h ~ 16h, preferably 4h ~ 12h.In second segment, in 300 DEG C ~ 450 DEG C of temperature, preferably 320 DEG C ~ 420 DEG C items
The catalyst is contacted with oxygen-containing gas under part, time of contact is 2h ~ 14h, preferably 3h ~ 8h.Oxygen content in oxygen-containing gas
Generally 0.2v% ~ 25.0v%, preferably 0.5v% ~ 10.0v%.
In the method for the present invention, the reducibility gas that ability routine may be used in the reduction treatment is restored, preferably
It is restored using hydrogen, the hydrogen feed of 99.9 v % of purity ＞, the operation item of the reduction treatment may be used in hydrogen
Part is：The catalyst is contacted with hydrogen, temperature is 100 DEG C ~ 500 DEG C, preferably 200 DEG C ~ 450 DEG C；1.0 h of time ~
15.0h, preferably 5.0 h ~ 10.0h；Hydrogen Vapor Pressure is 0.5 MPa ~ 6.0MPa, preferably 1.0 MPa ~ 4.0MPa.
In the method for the present invention, the dilute acid soln includes organic acid and inorganic acid, and wherein organic acid includes such as acetic acid, first
Acid, acrylic acid, lactic acid, inorganic acid include such as dilute hydrochloric acid, dust technology and phosphoric acid,diluted.The dilute acid soln be preferably acetic acid and/
Or dust technology.The wt% of a concentration of 0.1 wt% of diluted acid ~ 10.0 wt%, preferably 0.1 wt% ~ 5.0.The chitosan is dilute
The wt% of a concentration of 0.5 wt% in acid ~ 20.0 wt%, preferably 1.0 wt% ~ 10.0.Catalyst after making charcoal is placed in vacuum
It is impregnated under environment or inert atmosphere, the addition of the dilute acid soln, which is subject to, submerges catalyst, the body with catalyst
Product is than preferably 2:1~5:1.The temperature of the immersion can be 30 DEG C ~ 120 DEG C, preferably 45 DEG C ~ 100 DEG C；Time can be with
For the h of 4.0 h ~ 20.0, the h of preferably 8.0 h ~ 15.0.
In the method for the present invention, after being impregnated under vacuum environment or inert atmosphere through the dilute acid soln containing chitosan, so
After be dried and roast.The wherein described drying condition：Temperature is room temperature ~ 300 DEG C, and the time is 1.0h ~ 48.0h.
The method of roasting is roasted under aerobic conditions, and the roasting condition can be：By the catalysis
Agent is contacted with oxygen-containing gas, 300 DEG C ~ 600 DEG C of temperature, preferably 350 DEG C ~ 550 DEG C, and time of contact is 1.0h ~ 10h, preferably
2.0h~8.0h.Oxygen content can be 0.2v% ~ 25v%, preferably 0.5v% ~ 10v% in oxygen-containing gas.
The method of the present invention has the following advantages that：
（1）First decaying catalyst is handled with organic solvent, the carbon deposit content on decaying catalyst can be reduced, favorably
Temperature when its regeneration is controlled, heat release is excessive when preventing from regenerating or excessively concentrates, and avoids the mistake thermal response of catalyst, causes to urge
Agent property changes, as the structure of molecular sieve is destroyed or the enrichment of carried metal causes to bear to the property of catalyst
Face is rung.
（2）Regeneration temperature and oxygen content are strictly controlled in program-controlled coke combustion, this is because containing higher in catalyst
The TON type molecular sieves of ratio, due to the particularity of its molecular sieve（It is easily converted to the more stable ZSM-5 molecular sieve knot of structure
Structure）, charcoal temperature is excessively high, seriously affects the crystallinity of molecular sieve, and researches show that charcoal temperatures in the knot of 420 DEG C of procatalyst
Structure does not have a significant change, but when 450 DEG C of charcoal temperature, apparent variation, same fresh catalyst has occurred in the structure of catalyst
It compares, relative crystallinity drops to 97%（Fig. 1 is fresh dose of XRD diagram）, so in burning process is aoxidized, charcoal temperature is
One key factor.When charcoal temperature is relatively low, carbon deposit elimination factor is relatively low, but with the raising of charcoal temperature, can cause activity
The aggregation of metal and the structure for destroying molecular sieve, make the performance of catalyst be a greater impact.In entire regenerative process, it is necessary to
The temperature of stringent control catalyst particle surface is excessively high, and ensures that oxidation is thorough, but due to during making charcoal, catalyst
On carbon heat is also released during burning, so consider for ensure catalyst be not burned control temperature 450
Below DEG C.
（3）Load a certain amount of nickel compound containing on program-controlled procatalyst of making charcoal, and under relatively low regeneration temperature into
Row coke-burning regeneration since nickel can be acted on the acid centre of catalyst, reduces acid strength, so as to reduce the work of carrier and carbon deposit
With, cause carbon deposit be easier removed by oxidation, be not only able to remove effectively carbon deposit, and the nickel energy in coke combustion in this way
The effective aggregation for avoiding noble metal, improves the dispersion of noble metal platinum, while avoids the destruction of TON type molecular sieve structures, carries
The hydrogenation/dehydrogenation reactivity of high catalyst, the performance recovery for making catalyst are horizontal to fresh catalyst.
（4）It makes charcoal that treated through program-controlled decaying catalyst carries out immersion treatment again, soak is contains the dilute of chitosan
Acid solution most obtains the catalyst of activation recovering through dry and calcination process afterwards.The method of the present invention is organic by adding in chitosan
Object because containing a large amount of more active hydroxyl and amino in its chitosan molecule structure, is combined, energy and catalyst by coordinate bond
The Pt metal and Ni on surface, particularly nickel form fabulous high-molecular chelating agent, after dry and calcination process, can make catalysis
The metal platinum nickel on agent surface is disperseed well, is improved the hydrogenation/dehydrogenation reactivity of catalyst, is catalyzed after making regenerating reactivating
Its isomerization reaction performance of agent can be restored to fresh catalyst level.
Description of the drawings
Fig. 1 is the XRD spectra of fresh dose of FD-1（100%）；
Fig. 2 is the XRD spectra of deactivator FD-1（Crystallinity ~ 99%）；
Fig. 3 is the XRD spectra of R-420（Crystallinity ~ 99%）；
Fig. 4 is the XRD spectra of R-450（Crystallinity ~ 97%）；
Fig. 5 is the XRD spectra of R-500（Crystallinity ~ 92%）.
Wherein, the R- in Fig. 3-5 refers to that the calcination temperature of FD-1 deactivators, such as R-420 represent FD-1 deactivators through 420
After DEG C calcination process, the digitized representation relative crystallinity in bracket.
Specific embodiment
The preparation process of catalyst, but it is not considered that the present invention only office are further illustrated the present invention below by embodiment
It is limited in following embodiment.In the present invention, wt% is mass fraction, and v% is volume fraction.
Regenerated catalyst of the present invention is evaluated using the medium-sized fixed bed reactors of 200mL, and loaded catalyst is
100mL carries out prereduction to catalyst before charging, the noble metal on catalyst is made to be changed into reduction-state, reducing condition is as follows：
In the presence of hydrogen, 300 DEG C ~ 500 DEG C, pressure 0.5MPa ~ 10MPa, time 1.0h ~ 12.0h of temperature, feedstock oil used in evaluation
Main character is shown in Table 1.
1 feedstock oil main character of table
| Density（20℃）, kg/m3 | 861.1 |
| Sulphur, μ g/g | 4.0 |
| Nitrogen, μ g/g | 1.2 |
| Viscosity（40℃）, 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 present invention relates to FD-1 decaying catalysts hydrogen is added to split in Sinopec Qilu Petrochemical for FD-1 fresh catalysts
Change the deactivator after tail oil isomerization dewaxing device industrial operation.The physico-chemical property of FD-1 decaying catalysts is as follows：Specific surface area is
103m2/ g, Kong Rongwei 0.28mL/g, Pt content 0.45wt%, C content are 7.24 wt %.The composition and property that fresh dose of FD-1
It is as follows：Specific surface area is 235m2The content of/g, Kong Rongwei 0.35mL/g, Pt content 0.50wt%, ZSM-22 molecular sieve is
70wt%。
The physico-chemical property of FD-2 decaying catalysts of the present invention is as follows：Specific surface area is 110m2/ g, Kong Rongwei
0.26mL/g, Pt content 0.45wt%, C content are 8.12wt %.The composition and property that fresh dose of FD-2 are as follows：Specific surface area is
245m2The content of/g, Kong Rongwei 0.36mL/g, Pt content 0.50wt%, NU-10 molecular sieve is 50wt%.
The physico-chemical property of FD-3 decaying catalysts of the present invention is as follows：Specific surface area is 120m2/ g, Kong Rongwei
0.27mL/g, Pt content 0.44wt%, C content are 10.02wt %.The composition and property that fresh dose of FD-3 are as follows：Specific surface area is
270m2The content of/g, Kong Rongwei 0.37mL/g, Pt content 0.50wt%, SSZ-32 molecular sieve is 40wt%.
Wherein FD-2 and FD-3 is laboratory rapid deactivation agent.
Embodiment 1
The preparation of catalyst E-1 of the present invention.
1450mL organic solvents are added in the flask of 2000mL（Wherein ethyl alcohol and benzene volume ratio are 2:1）, to 200mL works
Decaying catalyst FD-1 processing after industry operating, it is Ca-1 to distill the catalyst number after 2.0h.
Ca-1 catalyst 100g are taken, add in 11.8g nickel nitrates（Nickel content 3.0wt%）It is impregnated in solution, is made Ni's and Pt
Atomic ratio is about 3:1 nickeliferous sample, then carry out in the atmosphere of air it is program-controlled make charcoal, the specific steps are with the liter of 3 DEG C/min
Warm speed is warming up to 250 DEG C of constant temperature 10h, then proceedes to the heating rate of 3 DEG C/min, is warming up to 410 DEG C of constant temperature 3h, obtains this
Invention catalyst Ea-1.
Above-mentioned catalyst Ea-1 reduction treatments under an atmosphere of hydrogen, actual conditions are：Hydrogen Vapor Pressure is 3.5MPa, reduction temperature
It is 430 DEG C to spend, recovery time 6h.
Treated catalyst is placed in vacuum impregnation device, addition contains chitosan（Deacetylation ＞ 80%, under
Together）Dilute nitric acid solution in, a concentration of 1.5 wt % of dust technology in the solution.A concentration of 2.6 wt % of chitosan,
The volume ratio of catalyst and solution is 1:2.5, soaking temperature is 45 DEG C, soaking time 10.0h.
Rear catalyst is impregnated to be filtered, then through 120 DEG C of dry 10h, then roasted under air atmosphere, specific item
Part is with the heating rate of 3 DEG C/min, is warming up to 500 DEG C of roasting 3h, obtains catalyst E-1 of the present invention.Its physico-chemical property is shown in Table 2,
Reaction result is shown in Table 3.
Embodiment 2
The preparation of catalyst E-2 of the present invention.
1450mL organic solvents are added in the flask of 2000mL（Wherein ethyl alcohol and benzene volume ratio are 1:1）To 200mL works
Decaying catalyst FD-1 processing after industry operating, it is Ca-2 to distill the catalyst number after 2h.
Ca-2 catalyst 100g are taken, add in 7.38g nickel acetates（Nickel content 8.0wt%）It is impregnated in solution, nickeliferous sample is made
The atomic ratio of product, wherein Ni and Pt is about 5:1, then carry out in the atmosphere of air it is program-controlled make charcoal, the specific steps are with 3 DEG C/min
Heating rate, be warming up to 240 DEG C of constant temperature 10h, then proceed to the heating rate of 3 DEG C/min, be warming up to 420 DEG C of constant temperature 3h,
Gained catalyst number is Eb-1.
Above-mentioned catalyst Eb-1 reduction treatments under an atmosphere of hydrogen, actual conditions are：Hydrogen Vapor Pressure is 4.5MPa, reduction temperature
It is 480 DEG C to spend, recovery time 5.0h.
It is placed in above-mentioned in vacuum impregnation device through reduction treatment rear catalyst, adds in the dilute acetic acid solution containing chitosan
In, a concentration of 2.6 wt% of spirit of vinegar in the solution.The volume of a concentration of 3.3 wt% of chitosan, catalyst and solution
It is 1:4, soaking temperature is 45 DEG C, soaking time 10h.
Rear catalyst is impregnated to be filtered, then through 110 DEG C of dry 10h, then roasted under air atmosphere, specific item
Part is with the heating rate of 3 DEG C/min, is warming up to 480 DEG C of roasting 3h, obtains catalyst E-2 of the present invention.Its physico-chemical property is shown in Table 2,
Reaction result is shown in Table 3.
Embodiment 3
The preparation of catalyst E-3 of the present invention.
1450mL organic solvents are added in the flask of 2000mL（Wherein gasoline and kerosene volume ratio are 1:1）, it is right
Decaying catalyst FD-1 processing after 200mL industrial operations, it is Cb-1 to distill the catalyst number after 2.0h.
Cb-1 catalyst 100g are taken, add in 35.4g nickel sulfates（Ni contents 2.0wt%）It is impregnated in solution, nickeliferous sample is made
The atomic ratio of product, wherein Ni and Pt is about 6:1, then carry out in the atmosphere of air it is program-controlled make charcoal, the specific steps are with 3 DEG C/min
Heating rate, be warming up to 280 DEG C of constant temperature 8h, then proceed to the heating rate of 3 DEG C/min, be warming up to 350 DEG C of constant temperature 5h, obtain
Catalyst Ec-1 of the present invention.
Under an atmosphere of hydrogen through reduction treatment, actual conditions are above-mentioned catalyst Ec-1：Hydrogen Vapor Pressure is 2.5MPa, reduction
Temperature is 450 DEG C, recovery time 7.0h.
It is placed in above-mentioned in vacuum impregnation device through reduction treatment rear catalyst, adds in the dilute nitric acid solution containing chitosan
In, a concentration of 3.0wt% of dust technology in the solution.The volume of a concentration of 4.5wt% of chitosan, catalyst and solution is
1:5, soaking temperature is 45 DEG C, soaking time 10h.
Rear catalyst is impregnated to be filtered, then through 120 DEG C of dry 10h, then roasted under air atmosphere, specific item
Part is with the heating rate of 3 DEG C/min, is warming up to 450 DEG C of roasting 3h, obtains catalyst E-3 of the present invention.Its physico-chemical property is shown in Table 2,
Reaction result is shown in Table 3.
Embodiment 4~6
The preparation of catalyst E-4 ~ E-6 of the present invention.
For the preparation process of catalyst E-4 ~ E-6 of the present invention with embodiment 1, the difference lies in be catalyzed with inactivation used
Agent and nickel solution and diluted acid are with chitosan solution concentration difference, the catalyst E-4 ~ E-6 of the present invention prepared, physico-chemical property
2 are shown in Table, reaction result is shown in Table 3.
Comparative example 1
It is prepared by comparative catalyst C-1 of the present invention.
The preparation method is the same as that of Example 1 for catalyst, the difference lies in catalyst without nickel solution processing procedure, number
For C-1, physico-chemical property is shown in Table 2, and reaction result is shown in Table 3.
Comparative example 2
It is prepared by comparative catalyst C-2 of the present invention.
The preparation method is the same as that of Example 1 for catalyst, makes charcoal and hydrogen reducing processing through program-controlled the difference lies in catalyst,
But handled without chitosan-containing dilute acid soln, number C-2, physico-chemical property is shown in Table 2, and reaction result is shown in Table 3.
Comparative example 3
It is prepared by comparative catalyst C-3 of the present invention.
The preparation method is the same as that of Example 1 for catalyst, though the difference lies in catalyst by it is program-controlled make charcoal, chitosan it is molten
Liquid, but handled without hydrogen reducing.Number is C-4, and physico-chemical property is shown in Table 2, and reaction result is shown in Table 3.
The treatment conditions of 2 each embodiment of table and comparative example
Table 2 continues each embodiment and the treatment conditions of comparative example
| Number | Solution treatment-diluted acid, wt% | Solution treatment-chitosan, wt% |
| E-1 | 1.5⑤ | 2.6 |
| E-2 | 2.6⑥ | 3.3 |
| E-3 | 3.0⑤ | 4.5 |
| E-4③ | 3.7⑥ | 6.2 |
| E-5 | 2.2⑤ | 7.1 |
| E-6④ | 3.1⑥ | 5.9 |
| C-1 | 2.8⑥ | 5.6 |
| C-2 | -- | -- |
| C-3 | 1.5⑤ | 2.6 |
Note：Ethyl alcohol/benzene, 2. gasoline/kerosene, 3. FD-2 decaying catalysts, 4. FD-3 decaying catalysts, 5. nitric acid, 6.
Acetic acid
3 evaluating catalyst condition of table and result
Table 3 continues evaluating catalyst condition and result
The evaluation result of table 3 is shown, compared with comparative catalyst, using catalyst provided by the invention, for lubricating oil
In the hydroprocessing processes of fraction, when lube base oil pour point is close, the catalyst activity after regeneration has reached fresh dose
Level, compared with contrast medium, C5 +Liquid, which is received, improves 10wt% or so, and lube base oil yield improves 5wt% or so, the viscosity of product
Index improves more than 10 units, illustrates catalyst of the present invention during crude lube stock is handled, and effect, which has, to be significantly improved.
By Fig. 1 to Fig. 5 as it can be seen that the crystallinity of fresh dose of FD-1, which is set to 100%, XDR structures, sees Fig. 1, the structure of deactivator
See Fig. 2, different charcoal temperatures（420 DEG C, 450 DEG C and 500 DEG C）The XRD characterization result of obtained sample is shown in Fig. 3 ~ Fig. 5, from Fig. 3
Result can be seen that：There is no significant change in the structure of 420 DEG C of procatalyst, but when charcoal temperature 450 in charcoal temperature
DEG C when, some changes have occurred in the structure of catalyst, and when charcoal temperature reaches 500 DEG C, the structure of catalyst has occurred significantly
Variation.Therefore, the present invention claims charcoal temperatures to control at 450 DEG C hereinafter, preferably below 420 DEG C.
Claims (26)
1. a kind of regeneration method of decaying catalyst, which includes TON types molecular sieve and the VIIIth race's noble metal component, regeneration
Process includes：Decaying catalyst is first handled with organic solvent, loads nickeliferousization using infusion process on catalyst after treatment
Object is closed, the nickel in the nickel compound containing wherein loaded on catalyst is 6 with pt atom ratio:1~1:1, then make in oxygen-containing gas
Under, progress is program-controlled to make charcoal, and the maximum temperature of coke combustion is not higher than 450 DEG C；Will treated catalyst under a reducing atmosphere
Carry out reduction treatment；Then it impregnates through the dilute acid soln containing chitosan in vacuum environment or inert atmosphere, is finally done
Dry and calcination process obtains the catalyst of activation recovering.
2. according to the method for claim 1, it is characterised in that：In the catalyst, noble metal component is platinum, TON types
Molecular sieve is one or more of ZSM-22, Nu-10, KZ-2 and ISI-1.
3. according to the method described in claims 1 or 2, it is characterised in that：In the catalyst, contain TON types 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 0.05wt%~5.0wt%, and surplus is refractory porous inorganic oxide.
4. according to the method for claim 3, it is characterised in that：On the basis of the weight of catalyst, the content of molecular sieve is
Preferably 30wt%~80wt%.
5. according to the method described in claims 1 or 2, it is characterised in that：The catalyst is hydroisomerization dewaxing catalyst.
6. according to the method described in claims 1 or 2, it is characterised in that：Nickel in the nickel compound containing loaded on catalyst with
The atomic ratio of platinum is 6:1~2:1.
7. according to the method for claim 6, it is characterised in that：Nickel and platinum in the nickel compound containing loaded on catalyst
Atomic ratio is 4:1~2:1.
8. according to the method described in claims 1 or 2, it is characterised in that：Decaying catalyst is first handled with organic solvent,
Used in organic solvent it is one or more in ethyl alcohol, benzene, gasoline and kerosene.
9. according to the method described in claims 1 or 2, it is characterised in that：Decaying catalyst is first handled with organic solvent,
The method of middle organic solvent processing decaying catalyst is using the method impregnated or distilled.
10. according to the method for claim 1, it is characterised in that：The volume ratio of organic solvent and catalyst is 8:1~1:1.
11. according to the method described in claims 1 or 2, it is characterised in that：Nickel compound containing, infusion process are loaded using infusion process
Maceration extract used is the aqueous solution of nickel compound containing, and concentration is calculated as 1.0wt%~10.0wt%, wherein nickel chemical combination with nickel element
Object is nickel nitrate, one or more in nickel acetate, nickel sulfate.
12. according to the method described in claims 1 or 2, it is characterised in that：Program-controlled make charcoal is made charcoal using two sections, wherein first segment
In, the catalyst is contacted with oxygen-containing gas under the conditions of 150 DEG C~280 DEG C of temperature, time of contact is 2h~16h, second
Duan Zhong contacts the catalyst with oxygen-containing gas under the conditions of 300 DEG C~450 DEG C of temperature, and time of contact is 2h~14h.
13. according to the method described in claims 1 or 2, it is characterised in that：Program-controlled make charcoal is made charcoal using two sections, wherein first segment
In, the catalyst is contacted with oxygen-containing gas under the conditions of 190 DEG C~280 DEG C of temperature, time of contact is 4h~12h, second
Duan Zhong contacts the catalyst with oxygen-containing gas under the conditions of 320 DEG C~420 DEG C of temperature, and time of contact is 3h~8h.
14. according to the method described in claims 1 or 2, it is characterised in that：Oxygen content is 0.2v%~15.0v% in oxygen-containing gas.
15. according to the method for claim 14, it is characterised in that：Oxygen content is 0.5v%~10.0v% in oxygen-containing gas.
16. according to the method for claim 1, it is characterised in that：The operating condition of the reduction treatment is：It is urged described
Agent is contacted with hydrogen, and temperature is 100 DEG C~500 DEG C；Time is 1h~15h；Hydrogen Vapor Pressure is 0.5MPa~6.0MPa.
17. according to the method for claim 16, it is characterised in that：The operating condition of the reduction treatment is：By described in
Catalyst is contacted with hydrogen, and temperature is 200 DEG C~450 DEG C；Time is 5h~10h；Hydrogen Vapor Pressure is 1.0MPa~4.0MPa.
18. according to the method for claim 1, it is characterised in that：Dilute acid soln is included in the solution of organic acid and inorganic acid
It is one or more, wherein organic acid includes acetic acid, formic acid, acrylic acid, lactic acid, and inorganic acid includes dilute hydrochloric acid, dust technology and dilute
Phosphoric acid.
19. according to the method described in claim 1 or 18, it is characterised in that：Diluted acid is spirit of vinegar and/or dust technology.
20. according to the method described in claim 1 or 18, it is characterised in that：A concentration of 0.1wt% of the diluted acid in dilute acid soln
~10.0wt%；A concentration of 0.5 wt%~20.0wt% of the chitosan in dilute acid soln.
21. according to the method for claim 20, it is characterised in that：A concentration of 0.1wt% of the diluted acid in dilute acid soln~
5.0wt%；A concentration of 1.0wt%~10.0wt% of the chitosan in dilute acid soln.
22. according to the method for claim 1, it is characterised in that：The soaking temperature is 30 DEG C~120 DEG C；During immersion
Between for 4h~20h, the time is 8h~15h, and the volume ratio of dilute acid soln and catalyst is 2:1~5:1.
23. according to the method for claim 22, it is characterised in that：The soaking temperature is 45 DEG C~100 DEG C.
24. according to the method for claim 1, it is characterised in that：The drying condition：Temperature is room temperature~300 DEG C, when
Between be 1h~48h.
25. according to the method for claim 1, it is characterised in that：The roasting condition：By the catalyst with it is oxygenous
Body contacts, and temperature is 300 DEG C~600 DEG C, and time of contact is 1.0h~10h.
26. according to the method for claim 25, it is characterised in that：The roasting condition：By the catalyst with it is oxygen-containing
Gas contacts, and temperature is 350 DEG C~550 DEG C, and time of contact is 2.0h~8.0h.
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| CN113019472A (en) * | 2019-12-24 | 2021-06-25 | 中国石油天然气股份有限公司 | Regeneration method and application of deactivated transalkylation catalyst |
| CN113893872A (en) * | 2020-06-22 | 2022-01-07 | 中国石油化工股份有限公司 | Regeneration method of catalyst containing manganese oxide molecular sieve |
| CN113877625B (en) * | 2020-07-01 | 2023-10-31 | 中国石油化工股份有限公司 | Method for regenerating molecular sieve catalyst and application thereof |
| CN114425456B (en) * | 2020-10-09 | 2023-10-31 | 中国石油化工股份有限公司 | Regeneration method and application of olefin reduction catalyst |
| CN114425393B (en) * | 2020-10-29 | 2023-07-28 | 中国石油化工股份有限公司 | Preparation method of catalyst |
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