CN106179490B - A kind of regeneration method of decaying catalyst - Google Patents
A kind of regeneration method of decaying catalyst Download PDFInfo
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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, and regenerative process is as follows：Decaying catalyst first is handled with organic solvent, the atomic ratio of zinc supported on catalyst after treatment, zinc and platinum is 10:1~1:1, then under oxygen-containing gas effect, carry out it is program-controlled makes charcoal, the maximum temperature of coke combustion is not higher than 450 DEG C, will treated catalyst reduction treatment under an atmosphere of hydrogen；Then it is impregnated through the dilute acid soln containing chitosan in vacuum environment or inert atmosphere, most obtains the catalyst of activation recovering through dry and roasting afterwards.The method of the present invention is not only able to effectively remove carbon deposition removal at low temperature, ensures 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, containing noble metal and TON types more specifically to one kind
The regeneration method of the catalyst for hydroisomerizing of molecular sieve, the especially regeneration method of 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, hydroisomerization can effectively convert n-alkane to the isoparaffin of low condensation point, 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 are 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, cannot regenerate and 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 disadvantage is too many, seldom which is used to carry out catalyst regeneration.It is industrial at present, especially 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
It is also easy to produce hot-spot, 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 active fall 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 remains 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 is by the method for the used catalyst regeneration based on additive and activation：By the catalysis 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 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 for 80 ~ 500 DEG C with
And solubility in water is at least the organic additive contact of 5g/L, dries the institute so that at least 50wt% under certain condition
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 generally uses TON molecular sieves, is a kind of
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, cannot be as reforming catalyst into the chlorine of row metal
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 strictly control regeneration temperature and oxygen-containing 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
Handled by distinct methods to obtain preferably as a result, being conducive to control temperature when its regeneration, high temperature is reduced to catalyst
The influence of performance improves the activity of regenerated catalyst.Its processing mode is that carbon deposit cleaner such as propylene glycol monomethyl ether acetic acid is first added
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
Part is gone to be easy the carbon deposit removed, to reduce the heat released in coke-burning regeneration, but finally there is still a need for high temperature coke combustions, still
So there are problems that isomerization dewaxing catalyst is encountered in high temperature regeneration, especially aggregation, molecular sieve structure quilt occur for metal platinum
The problems such as destruction.
Invention content
In order to overcome shortcoming in the prior art, the present invention provides a kind of regeneration methods of decaying catalyst, especially
It is suitable for the catalyst recovery process of the molecular sieve and the VIIIth race's noble metal component of type containing TON, especially 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 present invention provides a kind of regeneration method of decaying catalyst, which includes TON types molecular sieve and the VIIIth race
Noble metal component, regenerative process include：Decaying catalyst is handled with organic solvent, negative using infusion process on catalyst after treatment
Zinc compound is carried, the zinc in the zinc compound wherein loaded on catalyst is 10 with pt atom ratio:1~1:1；Then containing
Under carrier of oxygen effect, progress is program-controlled to make charcoal, and the maximum temperature of coke combustion is not higher than 450 DEG C；By the catalyst after making charcoal also
Reduction treatment under former atmosphere；Then it impregnates through the dilute acid soln containing chitosan in vacuum environment or inert atmosphere, most passes through afterwards
Dry and roasting obtains 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 the content of preferably 30wt% ~ 80wt%, noble metal are 0.05% ~ 5.0%, the porous nothing of refractory
The content of machine 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 zinc compound may be used.Maceration extract used in infusion process, which uses, contains zinc
The aqueous solution of compound, zinc compound can be one kind in the soluble zinc salts such as zinc nitrate, zinc acetate, zinc chloride, zinc sulfate
Or a variety of, a concentration of 1.0wt% ~ 10.0wt% of the aqueous solution of zinc compound（In terms of Zn-ef ficiency）, wherein the load capacity of zinc with
Platinum content is related in decaying catalyst, and the atomic ratio of general Zn and Pt are 10:1~1:1, preferably 10:1~2:1, further preferably
It is 8:1~4:1.
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 that low temperature is made charcoal the stage, and second segment burns for high temperature
The charcoal stage.In first segment, by the catalyst and oxygen-containing gas under the conditions of 150 DEG C ~ 280 DEG C, preferably 190 DEG C ~ 280 DEG C of temperature
Contact, time of contact are 2h ~ 16h, preferably 4h ~ 12h.In second segment, in 300 DEG C ~ 450 DEG C, preferably 320 DEG C ~ 420 DEG C of temperature
Under the conditions of the catalyst is contacted with oxygen-containing gas, time of contact be 2h ~ 14h, preferably 3h ~ 8h.Oxygen contains in oxygen-containing gas
Amount is generally 0.2v% ~ 25.0v%, preferably 0.5v% ~ 10v%.
In the method for the present invention, the reduction treatment may be used reducibility gas commonly used in the art and be gone back
It is former, it is preferred to use hydrogen is restored, and hydrogen uses the hydrogen feed of 99.9 v % of purity ＞, the operation of the reduction treatment
Condition is：The catalyst is contacted with hydrogen, temperature be 100 DEG C ~ 500 DEG C, preferably 200 DEG C ~ 450 DEG C, the time be 1.0h ~
15.0h, preferably 5.0h ~ 10.0h, Hydrogen Vapor Pressure are 0.5 MPa ~ 6.0MPa, preferably 1.0 MPa ~ 4.0MPa.
In the method for the present invention, the dilute acid soln include it is one or more in the solution of organic acid and inorganic acid,
Middle organic acid includes such as acetic acid, formic acid, acrylic acid, lactic acid, and inorganic acid includes such as dilute hydrochloric acid, dust technology and phosphoric acid,diluted.Diluted acid is excellent
It is selected as acetic acid and/or dust technology.A concentration of 0.1wt% ~ 10.0wt% of diluted acid, preferably 0.1 wt% ~ 5.0wt%.The shell
Glycan a concentration of 0.5wt% ~ 20.0wt% in diluted acid, preferably 1.0wt% ~ 10.0wt%.Catalyst after making charcoal is placed in
It is impregnated in vacuum environment or inert atmosphere.The temperature of the immersion can be 30 DEG C ~ 120 DEG C, preferably 45 DEG C ~ 100
DEG C, soaking time can be 4h ~ 20h, and the addition of preferably 8.0h ~ 15.0h, the dilute acid soln are to submerge catalyst
Standard, the volume ratio with catalyst are preferably 2:1~5:1 .The temperature of the drying be 60 DEG C ~ 200 DEG C, preferably 80 DEG C ~ 150
DEG C, drying time 1h ~ 20h, preferably 3h ~ 15h.
Further include continuing to carry out hot place in vacuum environment or inert atmosphere between drying and roasting in the method for the present invention
The step of reason, is first heat-treated after the completion of dry, then is roasted.The heat treatment is in inert gas（Such as N2、
Ar etc.）Under atmosphere, the catalyst after impregnating, drying is heat-treated stage by stage, it is preferred to use be heat-treated in two stages：
First segment is the Low Temperature Heat Treatment stage, and second segment is the high-temperature heat treatment stage.The control condition of first stage：Temperature be 250 DEG C ~
350 DEG C, preferably 260 DEG C ~ 320 DEG C, the time is 1h ~ 2h；The control condition of second segment：Temperature is 420 DEG C ~ 520 DEG C, preferably
It it is 450 DEG C ~ 500 DEG C, the time is 2h ~ 4h.
In the method for the present invention, method of roasting commonly used in the art may be used in the method for roasting, is preferably having
It is roasted under the conditions of oxygen, the roasting condition can be：The catalyst is contacted with oxygen-containing gas, 300 DEG C of temperature ~
600 DEG C, preferably 350 DEG C ~ 550 DEG C, time of contact is 1.0h ~ 10h, preferably 2.0h ~ 8.0h.Oxygen content can in oxygen-containing gas
Think 0.2v% ~ 25v%, preferably 0.5v% ~ 10v%.
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 controlling its regeneration, 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 aoxidizing burning process, 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 also release heat during burning, so consider for ensure catalyst be not burned control temperature 450
DEG C or less.
（3）Load a certain amount of zinc compound on program-controlled procatalyst of making charcoal, and under lower regeneration temperature into
Row coke-burning regeneration, since zinc compound is easy to be restored by carbon at high temperature, and zinc is met oxygen and is easily oxidized, and is aoxidizing
It will produce active oxygen in journey, the carbon distribution that active oxygen can be quickly on oxidation catalyst generates carbon dioxide, is not only able in this way
Carbon deposit is removed effectively, and zinc is disperseed with the platinum formation zinc platinum alloy on decaying catalyst in coke combustion, can be had
The aggregation for avoiding noble metal of effect, improves the dispersion of noble metal platinum, while avoiding the destruction of TON type molecular sieve structures.
（4）Restore again processing and impregnation through program-controlled decaying catalyst of making charcoal that treated, maceration extract be containing
The dilute acid soln of chitosan, last thermally treated and calcination process, obtains the catalyst of activation recovering.The method of the present invention is by adding
Enter chitosan organic matter, because, containing a large amount of more active hydroxyl and amino, being bonded by being coordinated in its chitosan molecule structure
It closes, fabulous high-molecular chelating agent can be formed with the metal Zn-Pt of catalyst surface, can after heat treatment metal platinum be made to obtain very
Good dispersion, then make its isomerization reaction performance of regenerating reactivating rear catalyst that can restore to fresh catalyst by burning processing through high temperature
It is horizontal.And the zinc after reduction treatment is easy in dilute acid soln to react with acid, can be removed zinc by way of pickling.This
Sample not only can guarantee that the catalyst pore structure after regeneration is not destroyed, and metal platinum can be made to have preferably dispersibility, improve
The hydrogenation/dehydrogenation reactivity of catalyst, to keep the performance recovery of catalyst horizontal to fresh catalyst.
Description of the drawings
Fig. 1 is the XRD spectra of fresh dose of FD-1（100%）；
Fig. 2 is the XRD spectra of FD-1 deactivators（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-Fig. 5 refers to the calcination temperature of FD-1 deactivators, such as R-420 expression FD-1 deactivators warps
After 420 DEG C of calcination process, the number in bracket represents relative crystallinity.
Specific implementation mode
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 embodiment below.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, so that the noble metal on catalyst is 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 evaluates used feedstock oil
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 be FD-1 fresh catalysts add hydrogen to split in Sinopec Qilu Petrochemical
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 0.26
ML/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 120g are taken, 14.4g zinc nitrates are added（Zn contents 5.0wt%）It is impregnated in solution, is made Zn's and Pt
Atomic ratio is 4:1 sample containing Zn, then carry out in the atmosphere of air it is program-controlled make charcoal, the specific steps are with the heating of 3 DEG C/min
Speed is warming up to 250 DEG C of constant temperature 10h, then proceedes to, with the heating rate of 3 DEG C/min, be warming up to 410 DEG C of constant temperature 3h, gained is urged
Agent number is 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
Degree is 430 DEG C, recovery time 6.0h.
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.
It impregnates rear catalyst to be filtered, then through 120 DEG C of dry 10h, in N2Under atmosphere, catalyst successively carries out two ranks
The heat treatment of section, the control condition of first stage：Temperature is 300 DEG C, time 1h, the control condition of second stage：Temperature is
500 DEG C, time 3h, finally by treated, catalyst roasts under air atmosphere, and actual conditions are with 3 DEG C/min's
Heating rate is warming up to 450 DEG C of constant temperature 3h.Obtain catalyst E-1 of the present invention.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.
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 120g are taken, 8.8g zinc acetates are added（Zn contents 10.0wt%）It is impregnated in solution, the sample containing Zn is made
The atomic ratio of product, wherein Zn and Pt is 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's
Heating rate is warming up to 230 DEG C of constant temperature 10h, then proceedes to, with the heating rate of 3 DEG C/min, be warming up to 420 DEG C of constant temperature 3h, institute
It is Eb-1 to obtain catalyst number.
Above-mentioned catalyst Eb-1 reduction treatments under an atmosphere of hydrogen, actual conditions are：Hydrogen Vapor Pressure is 4.5MPa, reduction temperature
Degree is 480 DEG C, recovery time 5.0h.
It is placed in above-mentioned in vacuum impregnation device through reduction treatment rear catalyst, the dilute acetic acid solution containing chitosan is added
In, a concentration of 2.6 wt% of spirit of vinegar in the solution.A concentration of 3.3 wt% of chitosan, the volume of catalyst and solution
It is 1:4, soaking temperature is 45 DEG C, soaking time 10.0h.
It impregnates rear catalyst to be filtered, then through 110 DEG C of dry 8h, in N2Under atmosphere, two are successively carried out to catalyst
The heat treatment in stage, the control condition of first stage：Temperature is 300 DEG C, time 1h；The control condition of second stage is 480
DEG C, time 3h, finally by treated, catalyst roasts under air atmosphere, and actual conditions are with the liter of 3 DEG C/min
Warm speed is warming up to 500 DEG C of constant temperature 3h.Obtain catalyst E-2 of the present invention.Its physico-chemical property is shown in Table 2, and 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）, right
Decaying catalyst FD-1 processing after 200mL industrial operations, it is Cb-1 to distill the catalyst number after 2h.
Cb-1 catalyst 120g are taken, 70.5g zinc nitrates are added（Zn contents 2.0wt%）It is impregnated in solution, the sample containing Zn is made
The atomic ratio of product, wherein Zn and Pt is 8:1, then carry out in the atmosphere of air it is program-controlled make charcoal, the specific steps are with 3 DEG C/min's
Heating rate is warming up to 280 DEG C of constant temperature 8h, then proceedes to, with the heating rate of 3 DEG C/min, be warming up to 350 DEG C of constant temperature 5h, gained
Catalyst number is Ec-1.
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 7h.
It is placed in above-mentioned in vacuum impregnation device through reduction treatment rear catalyst, the dilute nitric acid solution containing chitosan is added
In, a concentration of 3.0 wt% of dust technology in the solution.A concentration of 4.5 wt% of chitosan, the volume of catalyst and solution
It is 1:5, soaking temperature is 45 DEG C, soaking time 10.0h.
It impregnates rear catalyst to be filtered, then through 120 DEG C of dry 10h, in N2Under atmosphere, two are successively carried out to catalyst
The heat treatment in stage, first stage：Temperature is 300 DEG C, and the time is 1 h, second stage：Temperature is 500 DEG C, time 3h, most
By treated, catalyst roasts under air atmosphere afterwards, and actual conditions are to be warming up to the heating rate of 3 DEG C/min
350 DEG C of constant temperature 3h.Obtain catalyst E-3 of the present invention.Its physico-chemical property is shown in Table 2, and reaction result is shown in Table 3.
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 is with embodiment 1, the difference is that being catalyzed with inactivation used
Agent and zinc solution and diluted acid different, the catalyst E-4 ~ E-6 of the present invention prepared, physico-chemical property with chitosan solution concentration
2 are shown in Table, reaction result is shown in Table 3.
Embodiment 7
It is prepared by catalyst E-7 of the present invention.
The preparation method is the same as that of Example 1 for catalyst, though the difference is that catalyst through it is program-controlled make charcoal, hydrogen reducing and shell
Glycan solution treatment, but without Overheating Treatment, number E-7, physico-chemical property is shown in Table 2, and 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 is that catalyst without zinc solution handle and roasting at
Reason process, number C-1, physico-chemical property are 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, the difference is that catalyst is made charcoal and hydrogen reducing processing through program-controlled,
But handle and be heat-treated 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 is that catalyst by it is program-controlled make charcoal, chitosan solution
And heat treatment, but handled without hydrogen reducing.Number is C-3, and physico-chemical property is shown in Table 2, and reaction result is shown in Table 3.
The treatment conditions of table 2 each embodiment and comparative example
| Number | Organic solvent volume ratio | Zn:Pt | Zinc solution | Program-controlled processing of making charcoal | Hydrogen Vapor Pressure, MPa | Reduction temperature |
| E-1 | 2:1① | 4:1 | 5 wt % zinc nitrates | 250℃×10h;410℃×3h | 3.5 | 430℃×6h |
| E-2 | 1:1① | 5:1 | 10 wt % zinc acetates | 230℃×10h;420℃×3h | 4.5 | 480℃×5h |
| E-3 | 1:1② | 8:1 | 2 wt % zinc nitrates | 280℃×8h;350℃×5h | 2.5 | 450℃×7h |
| E-4③ | 2:1① | 5:1 | 5 wt % zinc chloride | 250℃×10h;410℃×4h | 3.2 | 400℃×5h |
| E-5 | 1:1① | 4:1 | 4 wt % zinc sulfate | 250℃×12h;350℃×5h | 3.8 | 410℃×5h |
| E-6④ | 1:1② | 6:1 | 7 wt % zinc nitrates | 260℃×10h;400℃×3h | 4.0 | 270℃×10h |
| E-7 | 2:1① | 4:1 | 5 wt % zinc nitrates | 250℃×10h;410℃×3h | 3.5 | 430℃×6h |
| C-1 | 1:1① | -- | -- | 250℃×10h;10℃×3h | 3.8 | 400℃×5h |
| C-2 | 1:1① | 4:1 | 5 wt % zinc nitrates | 250℃×10h;410℃×3h | 3.5 | 350℃×6h |
| C-3 | 2:1① | 4:1 | 5 wt % zinc nitrates | 250℃×10h;410℃×3h | -- | -- |
Table 2 continues each embodiment and the treatment conditions of comparative example
| Number | Solution treatment-diluted acid, % | Solution treatment-chitosan, % | Heat treatment | Roasting |
| E-1 | 1.5⑤ | 2.6 | 300℃×1 h;500℃×3h | 450℃×3h |
| E-2 | 2.6⑥ | 3.3 | 300℃×1 h;480℃×3h | 500℃×3h |
| E-3 | 3.0⑤ | 4.5 | 300℃×1 h;500℃×3h | 350℃×3h |
| E-4③ | 3.7⑥ | 6.2 | 300℃×1 h;500℃×3h | 510℃×4h |
| E-5 | 2.2⑤ | 7.1 | 250℃×1 h;500℃×3h | 510℃×2h |
| E-6④ | 3.1⑥ | 5.9 | 300℃×1 h;510℃×3h | 500℃×5h |
| E-7 | 1.5⑤ | 2.6 | -- | 450℃×3h |
| C-1 | 2.8⑥ | 5.6 | 300℃×1 h;500℃×3h | -- |
| C-2 | -- | -- | -- | 450℃×3h |
| C-3 | 1.5⑤ | 2.6 | 300℃×1 h;500℃×3h | 450℃×3h |
Note：Ethyl alcohol/benzene, 2. gasoline/kerosene, 3. FD-2 decaying catalysts, 4. FD-3 decaying catalysts, 5. nitric acid, 6.
Acetic acid
FD-1 is current industrial regeneration agent, and FD-2 and FD-3 are laboratory rapid deactivation catalyst.
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, is used for lubricating oil
In the hydroprocessing processes of fraction, when lube base oil pour point is close, the catalyst after regeneration has reached fresh dose of level,
Compared with contrast medium, C5 +Liquid, which is received, improves 10wt% or more, and lube base oil yield improves 5wt% or more, the viscosity index (VI) of product
10 units or more are improved, illustrate catalyst of the present invention during handling crude lube stock, 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 in charcoal temperature, but works as charcoal temperature 450
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 obviously
Variation.Therefore, the present invention claims charcoal temperatures to control at 450 DEG C hereinafter, preferably at 420 DEG C or less.
Claims (28)
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, contains zinc impregnation using infusion process load on catalyst after treatment
Object is closed, the zinc in the zinc compound wherein loaded on catalyst is 10 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；Under a reducing atmosphere by the catalyst after making charcoal
Carry out reduction treatment；Then it is impregnated through the dilute acid soln containing chitosan in vacuum environment or inert atmosphere, most afterwards through drying
The catalyst of activation recovering is obtained with roasting.
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 method as claimed in claim 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 the wt% of 0.05 wt% ~ 5.0, 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
30wt%~80wt%。
5. according to method as claimed in claim 1 or 2, it is characterised in that：The catalyst is hydroisomerization dewaxing catalyst.
6. according to method as claimed in claim 1 or 2, it is characterised in that：Zinc in the zinc compound loaded on catalyst with
The atomic ratio of platinum is 10:1~2:1.
7. according to the method for claim 6, it is characterised in that：Zinc and platinum in the zinc compound loaded on catalyst
Atomic ratio is 8:1~4:1.
8. according to method as claimed in claim 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 method as claimed in claim 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 method as claimed in claim 1 or 2, it is characterised in that：Zinc compound, infusion process are loaded using infusion process
Maceration extract used uses the aqueous solution of zinc compound, concentration to be calculated as 1.0wt% ~ 10.0wt%, wherein zinc impregnation with Zn-ef ficiency
Conjunction object is one or more in zinc nitrate, zinc acetate, zinc chloride, zinc sulfate.
12. according to the method for claim 1, it is characterised in that：Program-controlled make charcoal is made charcoal using two sections, wherein in first segment,
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, in second segment,
The catalyst is contacted with oxygen-containing gas under the conditions of 300 DEG C ~ 450 DEG C of temperature, time of contact is 2h ~ 14h.
13. according to the method for claim 1, it is characterised in that：Program-controlled make charcoal is made charcoal using two sections, wherein in first segment,
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, in second segment,
The catalyst is contacted with oxygen-containing gas under the conditions of 320 DEG C ~ 420 DEG C of temperature, time of contact is 3h ~ 8h.
14. according to the method described in claim 12 or 13, it is characterised in that：In oxygen-containing gas oxygen content be 0.2v% ~
25.0v%。
15. according to the method for claim 14, it is characterised in that：Oxygen content is 0.5v% ~ 10v% 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, and the time is 1h ~ 15h, and 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：It will be described
Catalyst is contacted with hydrogen, and temperature is 200 DEG C ~ 450 DEG C, time 5h ~ 10h, and Hydrogen Vapor Pressure is 1.0 MPa ~ 4.0MPa.
18. according to the method for claim 1, it is characterised in that：Dilute acid soln includes in the solution of organic acid and inorganic acid
It is one or more, wherein organic acid includes acetic acid, formic acid, acrylic acid and 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 for claim 1, it is characterised in that：A concentration of 0.1wt% of the diluted acid in dilute acid soln ~
10.0wt%；A concentration of 0.5wt% ~ 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 1.0 wt%s ~ 10.0wt% of the chitosan in dilute acid soln.
22. according to the method for claim 1, it is characterised in that：The temperature of the immersion is 30 DEG C ~ 120 DEG C, when immersion
Between be 4h ~ 20h；The temperature of the drying is 60 DEG C ~ 200 DEG C, and drying time is 1h ~ 20h.
23. according to the method for claim 22, it is characterised in that：The temperature of the immersion is 45 DEG C ~ 100 DEG C, is impregnated
Time is 8h ~ 15h；The temperature of the drying is 80 DEG C ~ 150 DEG C, and drying time is 3h ~ 15h.
24. according to the method for claim 1, it is characterised in that：Further include continuing in vacuum ring between drying and roasting
The step of being heat-treated in border or inert atmosphere.
25. according to the method for claim 24, it is characterised in that：The heat treatment be under inert gas atmosphere, it is right
Impregnated catalyst is handled in two stages, the control condition of first stage：Temperature be 250 DEG C ~ 350 DEG C, the time be 1h ~
2h；The control condition of second segment：Temperature is 420 DEG C ~ 520 DEG C, and the time is 2h ~ 4h.
26. according to the method for claim 25, it is characterised in that：The control condition of first stage：Temperature is 260 DEG C ~ 320
DEG C, the time is 1h ~ 2h；The control condition of second segment：Temperature is 450 DEG C ~ 500 DEG C, and the time is 2h ~ 4h.
27. according to the method for claim 1, it is characterised in that：The condition of the roasting is：By the catalyst with contain
Carrier of oxygen contacts, and temperature is 300 DEG C ~ 600 DEG C, and the time is 1.0h ~ 10h.
28. according to the method for claim 27, it is characterised in that：The condition of the roasting is：By the catalyst with
Oxygen-containing gas contacts, and temperature is 350 DEG C ~ 550 DEG C, and the time is 2.0h ~ 8.0h.
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| CN113019445B (en) * | 2019-12-25 | 2023-10-10 | 中国石油化工股份有限公司 | Modified hydrotreating catalyst carrier, catalyst, preparation method and application thereof |
| CN113019407B (en) * | 2019-12-25 | 2023-10-10 | 中国石油化工股份有限公司 | Hydrotreating catalyst, preparation method and application thereof |
| CN113019406B (en) * | 2019-12-25 | 2023-11-07 | 中国石油化工股份有限公司 | Method for preparing hydrotreating catalyst |
| 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 |
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