CN106179490A

CN106179490A - A kind of renovation process of decaying catalyst

Info

Publication number: CN106179490A
Application number: CN201510210626.XA
Authority: CN
Inventors: 徐会青; 刘全杰; 贾立明; 王伟
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2015-04-29
Filing date: 2015-04-29
Publication date: 2016-12-07
Anticipated expiration: 2035-04-29
Also published as: CN106179490B

Abstract

The invention discloses the renovation process of a kind of decaying catalyst.This catalyst includes TON type molecular sieve and the VIIIth race's noble metal component, regenerative process is as follows: first process decaying catalyst with organic solvent, zinc supported on catalyst after treatment, zinc is 10:1 ~ 1:1 with the atomic ratio of platinum, then under oxygen-containing gas effect, carrying out program control making charcoal, the maximum temperature of coke combustion is not higher than 450 DEG C, the catalyst reduction treatment under an atmosphere of hydrogen after processing；Then soaking through the dilute acid soln containing chitosan in vacuum environment or inert atmosphere, last drying and roasting obtain the catalyst of activation recovering.The inventive method is not only able to the most effectively remove carbon deposit, it is ensured that catalyst pore structure is not destroyed, and noble metal dispersion can be made good, and the performance of regenerated catalyst is recovered very well.

Description

A kind of renovation process of decaying catalyst

Technical field

The present invention relates to the renovation process of a kind of decaying catalyst, more specifically, relate to a kind of containing noble metal with the renovation process of the catalyst for hydroisomerizing of TON type molecular sieve, the especially renovation process of paraffin hydrocarbon catalyst for hydroisomerizing, is particularly suitable for the catalyst recovery process that the hydroisomerization dewaxing process of lubricating oil uses.

Background technology

Isodewaxing Technology is mainly used in the hydrogen that faces of diesel oil, wax oil and other specialty oils and processes, and 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.In general, 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 the productivity of diesel oil, n-alkane can be converted into the isoparaffin of low condensation point by hydroisomerization effectively, and can also retain the feature of its high cetane number.High-quality extraordinary oil, hydroisomerization key technology especially is produced as the tail oil being hydrocracked about VGO or modifying.By the isomerization of long-chain normal paraffin, can produce the distillate component of low pour point, high viscosity index (HVI), low volatility, so exploitation isomerization dewaxing catalyst regeneration techniques not only has good economic benefit, and its social meaning is the most important and far-reaching.

The catalyst in use activity that oil-refining chemical process uses can be gradually lowered, i.e. catalysqt deactivation, is summed up reason and is 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 and collapse etc..The decaying catalyst caused for carbon deposit can recover its activity by regeneration method, and metal deposit is polluted to 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, as far as possible without steam and air, because steam can promote accumulation of metal on catalyst, zeolite crystalline structure to be destroyed.Owing to in-situ regeneration shortcoming is too many, which is seldom used to carry out catalyst regeneration.The most industrial, the catalyst in the most large-scale reactor all uses ex-situ regeneration technique.The major advantage of catalyst device outer regeneration technology is to be not likely to produce hot-spot in catalyst regeneration process, and catalyst activity recovery extent is higher；The natural law that goes into operation of device can be increased；And device reaction system is 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 carbon deposit on surface, i.e. makes catalyst regenerate by the way of making charcoal.Compared with fresh catalyst, the pore volume of regenerated catalyst, specific surface have a certain degree of decline, and the fall of activity is the biggest.

In order to improve the activity of regenerated catalyst, also certain methods is elaborated in patented technology, catalyst after regeneration is carried out post processing, propose to contact catalyst with additive such as CN1187215A and activate, being dried described catalyst the most under certain condition so that described additive remains substantially in catalyst, described additive is at least one compound of the compound selected from least two hydroxyl and 2 ~ 10 carbon atoms and the ether of these compounds.WO01/02092 describes a kind of in the following manner by the method for the regeneration of used catalyst based on additive with activation: contacted with oxygen-containing gas by this catalyst at maximum temperature is 500 DEG C, it is made to activate by contacting with organic additive subsequently, it is dried through uniform temperature again, to ensure that the described additive of at least 50% is maintained in this catalyst.Preferably additive is selected from comprising the oxygen-containing part of at least two and the compound of 2 ~ 10 carbon atoms and the compound derived by these compounds.Mentioned example includes acid, aliphatic diol, aliphatic diol ether, saccharide and oxygenatedchemicals.Method described in CN1890351A is: be 80 ~ 500 DEG C by catalyst and acid and boiling point and dissolubility in water is at least the organic additive of 5g/L and contact, dry under certain condition so that the described additive reservation of at least 50wt% in the catalyst.Above-mentioned ex-situ regeneration method, owing to make charcoal step through high temperature, processes with organic additive the most again, and 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 catalyst simultaneously containing noble metal and molecular sieve.This catalyst has suitable acid centre and high hydrogenation activity, its selective hydrocracking and hydroisomerization function is made to reach well to balance, wax isomerization reactivity and the selectivity that so can make catalyst are greatly improved, being 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: on (1) catalyst, carbon deposit covers the active sites of catalyst or plugs the duct of catalyst；(2) compound such as the sulfur in raw material, nitrogen makes catalyst poisoning；(3) gathering of metal or the destruction of carrier structure；(4) metal or nonmetallic deposition, such as silicon, arsenic, ferrum etc. in raw material.Owing to isomerization dewaxing catalyst is a kind of macromolecule sieve content noble metal catalyst, molecular sieve is a kind of metastable state crystallization, (such as high temperature under certain condition, illumination, long-time etc.) more stable structure (generally ZSM-5 molecular sieve structure) can be converted into, the reactivity worth of original catalyst can be lost, at high temperature easily lead to crystallization of molecular sieves structural damage, and it is easily caused the gathering of metal, once accumulation of metal, the chlorination that can not carry out metal as reforming catalyst updates (at high temperature, chlorine and steam are very big to the destruction of molecular sieve structure), even if using the conventional methods such as organic additive to process after making charcoal, it also is 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) renovation process is not suitable for the regeneration of isomerization dewaxing catalyst, in whole regenerative process, the temperature that must strictly control catalyst particle surface is too high, and ensure oxidation thoroughly, specially require strict control regeneration temperature and oxygen content in catalyst regeneration process for this.So isomerization dewaxing catalyst regeneration it is critical only that and finds a carbon deposit can tried one's best on Removal of catalyst, can suppress again molecular sieve to be destroyed and reduces the operating condition of accumulation of metal simultaneously.

In existing relevant deactivation catalyst of carbon deposit Recycling Patents, most of patents consider how emphatically to prevent decaying catalyst from concentrating in regenerative process or the problem of excessive exotherms.Such as US5,037,785 suggestion is under oxygen containing gas, and catalyst is devoked by the method using laser to irradiate, US4,202,865 suggestion batch (-type)s note oxygen, US4,780,195 and US4,417,975 grades are then thought and are added a certain amount of water in atmosphere to prevent sintering of catalyst etc..CN1768956A thinks that the carbon deposit on catalyst can process to obtain more preferable result by distinct methods, is conducive to controlling temperature during its regeneration, reduces the high temperature impact on catalyst performance, improves the activity of regenerated catalyst.Its processing mode is to be initially charged the carbon deposit cleaner such as organic solvent such as propylene glycol methyl ether acetate, propylene-glycol ethyl ether, dipropylene glycol methyl ether, propylene glycol monomethyl ether decaying catalyst is carried out washing by soaking.But the method solvent load is excessive, the macromole by-product in detergent is also difficult to separate.And the carbon deposit that the method first easily removes with organic solvent removing unit partial volume, to reduce the liberated heat when coke-burning regeneration, but finally remain a need for high temperature coke combustion, yet suffer from the problems such as the problem that isomerization dewaxing catalyst runs into, particularly metal platinum are assembled, molecular sieve structure is destroyed when high temperature regeneration.

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, it is particularly suited for containing TON type molecular sieve and the catalyst recovery process of the VIIIth race's noble metal component, the particularly renovation process of paraffin hydrocarbon hydroisomerization dewaxing catalyst.Using renovation process of the present invention, the most effectively remove carbon deposit, and can guarantee that catalyst duct is not destroyed, 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 invention provides the renovation process of a kind of decaying catalyst, this catalyst includes TON type molecular sieve and the VIIIth race's noble metal component, regenerative process includes: decaying catalyst organic solvent processes, use infusion process load zinc compound after treatment on catalyst, wherein on catalyst the ratio of zinc and the pt atom in the zinc compound of load for 10:1 ~ 1:1；Then under oxygen-containing gas effect, carrying out program control making charcoal, the maximum temperature of coke combustion is not higher than 450 DEG C；The reduction treatment under a reducing atmosphere of catalyst after making charcoal；Then soaking through the dilute acid soln containing chitosan in vacuum environment or inert atmosphere, last drying and roasting obtain the catalyst of activation recovering.

TON type molecular sieve in catalyst of the present invention, can be one or more in ZSM-22, SSZ-32, Nu-10, KZ-2 and ISI-1, preferably comprise ZSM-22 molecular sieve, and noble metal is selected from group VIII metal platinum.One or more in refractory porous inorganic oxide, such as aluminium oxide, silicon oxide, titanium oxide, zirconium oxide etc. can also be contained.On the basis of the weight of catalyst, the content of molecular sieve is 10wt% ~ 90wt%, preferably 30wt% ~ 80wt%, and the content of noble metal is 0.05% ~ 5.0%, and the content of refractory porous inorganic oxide is surplus.

In the inventive method, decaying catalyst first processes with organic solvent, organic solvent wherein used typically can use one or more in benzene, ethanol, gasoline, kerosene, and organic solvent processes the method that the method for decaying catalyst can use immersion, distillation etc. to commonly use.Organic solvent can be 8:1 ~ 1:1 with the volume ratio of catalyst.

In the inventive method, infusion process can be used to load zinc compound.Impregnation liquid used by infusion process uses the aqueous solution of zinc compound, zinc compound can be one or more in the soluble zinc salts such as zinc nitrate, zinc acetate, zinc chloride, zinc sulfate, the concentration of the aqueous solution of zinc compound is that 1.0wt% ~ 10.0wt%(is in terms of zinc element), wherein the load capacity of zinc is relevant with platinum content in decaying catalyst, the atomic ratio of general Zn Yu Pt is 10:1 ~ 1:1, preferably 10:1 ~ 2:1, more preferably 8:1 ~ 4:1.

In the inventive method, carrying out program control making charcoal under oxygen-containing gas effect, 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 paragraph is that low temperature is made charcoal the stage, second segment is that high temperature is made charcoal the stage.In first paragraph, temperature 150 DEG C ~ 280 DEG C, being contacted with oxygen-containing gas by described catalyst under the conditions of preferably 190 DEG C ~ 280 DEG C, time of contact is 2h ~ 16h, preferably 4h ~ 12h.In second segment, temperature 300 DEG C ~ 450 DEG C, being contacted with oxygen-containing gas by described catalyst under the conditions of preferably 320 DEG C ~ 420 DEG C, time of contact is 2h ~ 14h, preferably 3h ~ 8h.In oxygen-containing gas, oxygen content is generally 0.2v% ~ 25.0v%, preferably 0.5v% ~ 10v%.

In the inventive method, described reduction treatment can use reducibility gas commonly used in the art to reduce, preferably employing hydrogen to reduce, hydrogen uses the hydrogen feed of purity ＞ 99.9 v %, and the operating condition of described reduction treatment is: contacted with hydrogen by described catalyst, temperature is 100 DEG C ~ 500 DEG C, being preferably 200 DEG C ~ 450 DEG C, the time is 1.0h ~ 15.0h, preferably 5.0h ~ 10.0h, Hydrogen Vapor Pressure is 0.5 MPa ~ 6.0MPa, preferably 1.0 MPa ~4.0MPa。

In the inventive method, described dilute acid soln includes one or more in the solution of organic acid and mineral acid, and wherein organic acid includes such as acetic acid, formic acid, acrylic acid, lactic acid, and mineral acid includes such as dilute hydrochloric acid, dust technology and phosphoric acid,diluted.Diluted acid is preferably acetic acid and/or dust technology.The concentration of diluted acid is 0.1wt% ~ 10.0wt%, preferably 0.1 wt% ~ 5.0wt%.Described chitosan concentration in diluted acid is 0.5wt% ~ 20.0wt%, preferably 1.0wt% ~ 10.0wt%.Catalyst after making charcoal is placed in vacuum environment or inert atmosphere and soaks.The temperature of described immersion can be 30 DEG C ~ 120 DEG C, preferably 45 DEG C ~ 100 DEG C, and soak time can be 4h ~ 20h, preferably 8.0h ~ 15.0h, and the addition of described dilute acid soln is as the criterion with submergence catalyst, is preferably 2:1 ~ 5:1 with the volume ratio of catalyst.The described temperature being dried is 60 DEG C ~ 200 DEG C, preferably 80 DEG C ~ 150 DEG C, drying time 1h ~ 20h, preferably 3h ~ 15h.

In the inventive method, it is being dried the step also including continuing to carry out heat treatment in vacuum environment or inert atmosphere between roasting, after being dried, is i.e. first carrying out heat treatment, then carry out roasting.Described heat treatment is (such as N at noble gas₂, Ar etc.) under atmosphere, dipping, dried catalyst are carried out heat treatment stage by stage, it is preferred to use carrying out heat treatment in two stages: first paragraph is the Low Temperature Heat Treatment stage, second segment is the high-temperature heat treatment stage.The control condition of first stage: temperature is 250 DEG C ~ 350 DEG C, preferably 260 DEG C ~ 320 DEG C, and the time is 1h ~ 2h；The control condition of second segment: temperature is 420 DEG C ~ 520 DEG C, preferably 450 DEG C ~ 500 DEG C, and the time is 2h ~ 4h.

In the inventive method, described method of roasting can use method of roasting commonly used in the art, under aerobic conditions, preferably carry out roasting, described roasting condition may is that and contacted with oxygen-containing gas by described catalyst, temperature 300 DEG C ~ 600 DEG C, being preferably 350 DEG C ~ 550 DEG C, time of contact is 1.0h ~ 10h, preferably 2.0h ~ 8.0h.In oxygen-containing gas, oxygen content can be 0.2v% ~ 25v%, preferably 0.5v% ~ 10v%.

The inventive method has the advantage that

(1) first with organic solvent, decaying catalyst is processed, the carbon deposit content on decaying catalyst can be reduced, be conducive to controlling temperature during its regeneration, when preventing from regenerating, heat release too much or is excessively concentrated, avoid the mistake thermal response of catalyst, causing catalyst property to change, the structure such as molecular sieve is destroyed, or the character of catalyst is adversely affected by the enrichment of carried metal.

(2) strict control regeneration temperature and oxygen content in program control coke combustion, this is the TON type molecular sieve owing to containing higher proportion in catalyst, particularity (being easily converted to the ZSM-5 molecular sieve structure that structure is more stable) due to its molecular sieve, charcoal temperature is too high, have a strong impact on the degree of crystallinity of molecular sieve, research display charcoal temperature does not has significant change in the structure of the procatalyst of 420 DEG C, but when charcoal temperature 450 DEG C, the structure of catalyst there occurs significantly change, compared with fresh catalyst, it is the XRD figure of fresh dose that relative crystallinity drops to 97%(Fig. 1), so in oxidation burning process, charcoal temperature is a key factor.When charcoal temperature is relatively low, carbon deposit elimination factor is relatively low, but along with the rising of charcoal temperature, can cause assembling and the structure of saboteur's sieve of active metal, make the performance of catalyst be a greater impact.In whole regenerative process, the temperature that must strictly control catalyst particle surface is too high, and ensure that oxidation is thoroughly, but due to during making charcoal, carbon on catalyst also releases heat during burning, so considering for guaranteeing that catalyst is not burned control temperature below 450 DEG C.

(3) on program control procatalyst of making charcoal, a certain amount of zinc compound is loaded, and under relatively low regeneration temperature, carry out coke-burning regeneration, owing at high temperature zinc compound is easily reduced by carbon, and zinc is met oxygen and is easily oxidized, active oxygen can be produced in oxidizing process, active oxygen quickly can generate carbon dioxide by the carbon distribution on oxidation catalyst, so it is not only able to effectively remove carbon deposit, and zinc and the formation zinc platinum alloy of the platinum on decaying catalyst disperse in coke combustion, can effectively avoid the gathering of noble metal, improve the dispersion of noble metal platinum, avoid the destruction of TON type molecular sieve structure simultaneously.

(4) carrying out reduction treatment and impregnation process again through the program control decaying catalyst after processing of making charcoal, impregnation liquid is the dilute acid soln containing chitosan, and the most thermally treated and calcination process obtains the catalyst of activation recovering.The inventive method is by adding chitosan Organic substance, because containing substantial amounts of more active hydroxyl and amino in its chitosan molecule structure, combined by coordinate bond, fabulous high-molecular chelating agent can be formed with the metal Zn-Pt of catalyst surface, metal platinum after heat treatment can be made well to be disperseed, then burnt process through high temperature and make its isomerization reaction performance of regenerating reactivating rear catalyst can recover to fresh catalyst level.And the zinc after reduction treatment easily reacts with acid in dilute acid soln, zinc can be removed by the way of pickling.The most not only can guarantee that the catalyst pore structure after regeneration is not destroyed, and metal platinum can be made to have more preferable dispersibility, improve the hydrogenation/dehydrogenation reactivity of catalyst, so that the performance recovery of catalyst is to fresh catalyst level.

Accompanying drawing explanation

Fig. 1 is the XRD spectra (100%) of fresh dose of FD-1；

Fig. 2 XRD spectra (degree of crystallinity ~ 99%) for FD-1 deactivator；

Fig. 3 XRD spectra (degree of crystallinity ~ 99%) for R-420；

Fig. 4 XRD spectra (degree of crystallinity ~ 97%) for R-450；

Fig. 5 XRD spectra (degree of crystallinity ~ 92%) for R-500.

Wherein, the R-in Fig. 3-Fig. 5 refers to that the sintering temperature of FD-1 deactivator, such as R-420 represent FD-1 deactivator digitized representation relative crystallinity after 420 DEG C of calcination process, in bracket.

Detailed description of the invention

Further illustrate the preparation process of catalyst of the present invention below by embodiment, but invention should not be deemed limited in below example.In the present invention, wt% is mass fraction, and v% is volume fraction.

Regenerated catalyst of the present invention is to use the medium-sized fixed bed reactors of 200mL to be evaluated, loaded catalyst is 100mL, before Jin Liao, catalyst is carried out prereduction, the noble metal on catalyst is made to be changed into reduction-state, reducing condition is as follows: in presence of hydrogen, temperature 300 DEG C ~ 500 DEG C, pressure 0.5MPa ~ 10MPa, time 1.0h ~ 12.0h, evaluates the raw oil main character used and 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 FD-1 decaying catalyst that the present invention relates to is FD-1 fresh catalyst deactivator after Sinopec Qilu Petrochemical hydrocracking tail oil isomerization dewaxing device industrial operation.The physico-chemical property of FD-1 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 and character that FD-1 is fresh dose are as follows: specific surface area is 235m²/ g, pore volume is 0.35mL/g, Pt content 0.50wt%, and the content of ZSM-22 molecular sieve is 70wt%.

The physico-chemical property of the FD-2 decaying catalyst that the present invention relates to is as follows: specific surface area is 110m²/ g, pore volume is 0.26 mL/g, Pt content 0.45wt%, and C content is 8.12wt %.Composition and character that FD-2 is fresh dose are as follows: specific surface area is 245m²/ g, pore volume is 0.36mL/g, Pt content 0.50wt%, and the content of NU-10 molecular sieve is 50wt%.

The physico-chemical property of the FD-3 decaying catalyst that the present invention relates to is as follows: specific surface area is 120m²/ g, pore volume is 0.27mL/g, Pt content 0.44wt%, and C content is 10.02wt %.Composition and character that FD-3 is fresh dose are as follows: specific surface area is 270m²/ g, pore volume is 0.37mL/g, Pt content 0.50wt%, and the content of 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 solvent (wherein ethanol and benzene volume ratio are 2:1) is added, to decaying catalyst FD-1 process after 200mL industrial operation, the numbered Ca-1 of catalyst after distillation 2.0h in the flask of 2000mL.

Take Ca-1 catalyst 120g, add in 14.4g zinc nitrate (Zn content 5.0wt%) solution and impregnate, prepare Zn Yu Pt atomic ratio be 4:1 containing Zn sample, program control making charcoal is carried out again in the atmosphere of air, concretely comprise the following steps with the programming rate of 3 DEG C/min, be warming up to 250 DEG C of constant temperature 10h, then proceed to the programming rate of 3 DEG C/min, it is warming up to 410 DEG C of constant temperature 3h, the numbered Ea-1 of gained catalyst.

Above-mentioned catalyst Ea-1 reduction treatment under an atmosphere of hydrogen, actual conditions is: Hydrogen Vapor Pressure is 3.5MPa, and reduction temperature is 430 DEG C, recovery time 6.0h.

Being placed in vacuum impregnation device by catalyst after above-mentioned process, add in the dilute nitric acid solution containing chitosan (deacetylation ＞ 80%, lower same), in described solution, the concentration of dust technology is 1.5 wt %.The concentration of chitosan is 2.6 wt %, and catalyst is 1:2.5 with the volume ratio of solution, and soaking temperature is 45 DEG C, and soak time is 10.0h.

Soak rear catalyst to filter, then through 120 DEG C of dry 10h, at N₂Under atmosphere, catalyst successively carries out the heat treatment in two stages, the control condition of first stage: temperature is 300 DEG C, time is 1h, the control condition of second stage: temperature is 500 DEG C, the time is 3h, and the catalyst after finally processing carries out roasting under air atmosphere, actual conditions is with the programming rate of 3 DEG C/min, 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 solvent (wherein ethanol and benzene volume ratio are 1:1) is added, to decaying catalyst FD-1 process after 200mL industrial operation, the numbered Ca-2 of catalyst after distillation 2h in the flask of 2000mL.

Take Ca-2 catalyst 120g, add in 8.8g zinc acetate (Zn content 10.0wt%) solution and impregnate, prepare the sample containing Zn, wherein the atomic ratio of Zn Yu Pt is 5:1, then carries out program control making charcoal in the atmosphere of air, concretely comprises the following steps with the programming rate of 3 DEG C/min, it is warming up to 230 DEG C of constant temperature 10h, then proceed to the programming rate of 3 DEG C/min, be warming up to 420 DEG C of constant temperature 3h, the numbered Eb-1 of gained catalyst.

Above-mentioned catalyst Eb-1 reduction treatment under an atmosphere of hydrogen, actual conditions is: Hydrogen Vapor Pressure is 4.5MPa, and reduction temperature is 480 DEG C, recovery time 5.0h.

Being placed in above-mentioned in vacuum impregnation device through reduction treatment rear catalyst, add in the dilute acetic acid solution containing chitosan, in described solution, the concentration of spirit of vinegar is 2.6 wt%.The concentration of chitosan is 3.3 wt%, and catalyst is 1:4 with the volume of solution, and soaking temperature is 45 DEG C, and soak time is 10.0h.

Soak rear catalyst to filter, then through 110 DEG C of dry 8h, at N₂Under atmosphere, catalyst successively carrying out the heat treatment in two stages, the control condition of first stage: temperature is 300 DEG C, the time is 1h；The control condition of second stage is 480 DEG C, and the time is 3h, and the catalyst after finally processing carries out roasting under air atmosphere, and actual conditions is with the programming rate of 3 DEG C/min, 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 solvent (wherein gasoline and kerosene volume ratio are 1:1) is added, to decaying catalyst FD-1 process after 200mL industrial operation, the numbered Cb-1 of catalyst after distillation 2h in the flask of 2000mL.

Take Cb-1 catalyst 120g, add in 70.5g zinc nitrate (Zn content 2.0wt%) solution and impregnate, prepare the sample containing Zn, wherein the atomic ratio of Zn Yu Pt is 8:1, then carries out program control making charcoal in the atmosphere of air, concretely comprises the following steps with the programming rate of 3 DEG C/min, it is warming up to 280 DEG C of constant temperature 8h, then proceed to the programming rate of 3 DEG C/min, be warming up to 350 DEG C of constant temperature 5h, the numbered Ec-1 of gained catalyst.

Above-mentioned catalyst Ec-1 is under an atmosphere of hydrogen through reduction treatment, and actual conditions is: Hydrogen Vapor Pressure is 2.5MPa, and reduction temperature is 450 DEG C, recovery time 7h.

Being placed in above-mentioned in vacuum impregnation device through reduction treatment rear catalyst, add in the dilute nitric acid solution containing chitosan, in described solution, the concentration of dust technology is 3.0 wt%.The concentration of chitosan is 4.5 wt%, and catalyst is 1:5 with the volume of solution, and soaking temperature is 45 DEG C, and soak time is 10.0h.

Soak rear catalyst to filter, then through 120 DEG C of dry 10h, at N₂Under atmosphere, catalyst is successively carried out the heat treatment in two stages, first stage: temperature is 300 DEG C, time is 1 h, second stage: temperature is 500 DEG C, the time is 3h, and the catalyst after finally processing carries out roasting under air atmosphere, actual conditions is with the programming rate of 3 DEG C/min, is warming up to 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, difference is with decaying catalyst used different with chitosan solution concentration with zinc solution and diluted acid, catalyst E-4 ~ the E-6 of the present invention prepared, its physico-chemical property is shown in Table 2, and reaction result is shown in Table 3.

Embodiment 7

Prepared by catalyst E-7 of the present invention.

The preparation method of catalyst with embodiment 1, though difference be catalyst through program control making charcoal, hydrogen reducing and chitosan solution process, but without heat treatment, numbered E-7, its physico-chemical property is shown in Table 2, and reaction result is shown in Table 3.

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 processes and calcination process process without zinc solution, and numbered C-1, its physico-chemical property is shown in Table 2, and reaction result is shown in Table 3.

Comparative example 2

Prepared by comparative catalyst C-2 of the present invention.

The preparation method of catalyst is with embodiment 1, and difference is that catalyst is made charcoal and hydrogen reducing process through program control, but processes and heat treatment, numbered C-2 without chitosan-containing dilute acid soln, and its physico-chemical property is shown in Table 2, and reaction result is shown in Table 3.

Comparative example 3

Prepared by comparative catalyst C-3 of the present invention.

The preparation method of catalyst with embodiment 1, though difference be catalyst through program control making charcoal, chitosan solution and heat treatment, but process without hydrogen reducing.Numbered C-3, its physico-chemical property is shown in Table 2, and reaction result is shown in Table 3.

The each embodiment of table 2 and the treatment conditions of comparative example

Numbering

Organic solvent volume ratio

Zn:Pt

Zinc solution

Program control process of making charcoal

Hydrogen Vapor Pressure, MPa

Reduction temperature

E-1

2:1^①

4:1

5 wt % zinc nitrates

250℃×10h;410℃×3h

3.5

430℃×6h

E-2

1:1^①

5:1

10 wt % zinc acetates

230℃×10h;420℃×3h

4.5

480℃×5h

E-3

1:1^②

8:1

2 wt % zinc nitrates

280℃×8h;350℃×5h

2.5

450℃×7h

E-4^③

2:1^①

5:1

5 wt % zinc chloride

250℃×10h;410℃×4h

3.2

400℃×5h

E-5

1:1^①

4:1

4 wt % zinc sulfate

250℃×12h;350℃×5h

3.8

410℃×5h

E-6^④

1:1^②

6:1

7 wt % zinc nitrates

260℃×10h;400℃×3h

4.0

270℃×10h

E-7

2:1^①

4:1

5 wt % zinc nitrates

250℃×10h;410℃×3h

3.5

430℃×6h

C-1

1:1^①

--

250℃×10h;10℃×3h

3.8

400℃×5h

C-2

1:1^①

4:1

5 wt % zinc nitrates

250℃×10h;410℃×3h

3.5

350℃×6h

C-3

2:1^①

4:1

5 wt % zinc nitrates

250℃×10h;410℃×3h

--

Table 2 continues the treatment conditions of each embodiment and comparative example

Numbering	Solution process-diluted acid, %	Solution process-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-4^③	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-6^④	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: Ethanol/benzene, 2. gasoline/kerosene, 3. FD-2 decaying catalyst, 4. FD-3 decaying catalyst, 5. nitric acid, 6. acetic acid

FD-1 is current industrial regeneration agent, FD-2 and FD-3 is laboratory rapid deactivation catalyst.

Table 3 evaluating catalyst condition and result

Table 3 continues evaluating catalyst condition and result

The evaluation result of table 3 shows, compared with comparative catalyst, uses the catalyst that the present invention provides, and in the hydroprocessing processes of lube cut, when lube base oil pour point is close, the catalyst after regeneration has reached fresh dose of level, compared with contrast medium, C₅ ⁺Liquid is received and is improved more than 10wt%, and lube base oil yield improves more than 5wt%, and the viscosity index (VI) of product improves more than 10 units, illustrate catalyst of the present invention during process crude lube stock, effect has and significantly improves.

From Fig. 1 to Fig. 5, the degree of crystallinity that FD-1 is fresh dose is set to 100%, its XDR structure is shown in Fig. 1, the structure of deactivator is shown in Fig. 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 result of Fig. 3 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, when charcoal temperature reaches 500 DEG C, the structure of catalyst there occurs significantly change.Therefore, application claims charcoal temperature controls below 450 DEG C, preferably below 420 DEG C.

Claims

1. the renovation process of a decaying catalyst, 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, infusion process load zinc compound is used after treatment on catalyst, wherein on catalyst the ratio of zinc and the pt atom in the zinc compound of load for 10:1 ~ 1:1, then under oxygen-containing gas effect, carrying out program control making charcoal, the maximum temperature of coke combustion is not higher than 450 DEG C；Catalyst after making charcoal carries out reduction treatment under a reducing atmosphere；Then soaking through the dilute acid soln containing chitosan in vacuum environment or inert atmosphere, last drying and roasting obtain the catalyst of activation recovering.

The most in accordance with the method for claim 1, it is characterised in that: in described catalyst, noble metal component is platinum, and TON type molecular sieve is one or more in ZSM-22, SSZ-32, Nu-10, KZ-2 and ISI-1.

3. according to the method described in claim 1 or 2, it is characterized in that: in described catalyst, containing TON type molecular sieve, noble metal platinum and refractory porous inorganic oxide, on the basis of the weight of catalyst, the content of molecular sieve is 10wt% ~ 90wt%, being preferably 30wt% ~ 80wt%, the content of noble 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: described catalyst is hydroisomerization dewaxing catalyst.

5. according to the method described in claim 1 or 2, it is characterised in that: on catalyst, the zinc in the zinc compound of load is 10:1 ~ 2:1, preferably 8:1 ~ 4:1 with the atomic ratio of platinum.

6. according to the method described in claim 1 or 2, it is characterised in that: decaying catalyst first processes with organic solvent, one or more in ethanol, benzene, gasoline and kerosene of organic solvent wherein used.

7. according to the method described in claim 1 or 2, it is characterised in that: decaying catalyst first processes with organic solvent, and wherein organic solvent processes the method that the method employing of decaying catalyst is soaked or distilled.

The most in accordance with the method for claim 8, it is characterised in that: organic solvent is 8:1 ~ 1:1 with the volume ratio of catalyst.

9. according to the method described in claim 1 or 2, it is characterized in that: use infusion process load zinc compound, impregnation liquid used by infusion process uses the aqueous solution of zinc compound, its concentration is calculated as 1.0wt% ~ 10.0wt% with zinc element, one or more during wherein zinc compound is zinc nitrate, zinc acetate, zinc chloride, zinc sulfate.

The most in accordance with the method for claim 1, it is characterized in that: program control employing two sections of making charcoal is made charcoal, wherein in first paragraph, under the conditions of temperature 150 DEG C ~ 280 DEG C, described catalyst is contacted with oxygen-containing gas, time of contact is 2h ~ 16h, in second segment, being contacted with oxygen-containing gas by described catalyst under the conditions of temperature 300 DEG C ~ 450 DEG C, time of contact is 2h ~ 14h.

11. in accordance with the method for claim 1, it is characterized in that: program control employing two sections of making charcoal is made charcoal, wherein in first paragraph, under the conditions of temperature 190 DEG C ~ 280 DEG C, described catalyst is contacted with oxygen-containing gas, time of contact is 4h ~ 12h, in second segment, being contacted with oxygen-containing gas by described catalyst under the conditions of temperature 320 DEG C ~ 420 DEG C, time of contact is 3h ~ 8h.

12. according to the method described in claim 10 or 11, it is characterised in that: in oxygen-containing gas, oxygen content is generally 0.2v% ~ 25.0v%, preferably 0.5v% ~ 10v%.

13. in accordance with the method for claim 1, it is characterized in that: the operating condition of described reduction treatment is: contacted with hydrogen by described catalyst, temperature is 100 DEG C ~ 500 DEG C, it is preferably 200 DEG C ~ 450 DEG C, time is 1h ~ 15h, being preferably 5h ~ 10h, Hydrogen Vapor Pressure is 0.5MPa ~ 6.0MPa, preferably 1.0 MPa ~ 4.0MPa.

14. in accordance with the method for claim 1, it is characterised in that: dilute acid soln includes one or more in the solution of organic acid and mineral acid, and wherein organic acid includes acetic acid, formic acid, acrylic acid and lactic acid, and mineral acid includes dilute hydrochloric acid, dust technology and phosphoric acid,diluted.

15. according to the method described in claim 1 or 14, it is characterised in that: diluted acid is spirit of vinegar and/or dust technology.

16. in accordance with the method for claim 1, it is characterised in that: diluted acid concentration in dilute acid soln is 0.1wt% ~ 10.0wt%, preferably 0.1wt% ~ 5.0wt%；Chitosan concentration in dilute acid soln is 0.5wt% ~ 20.0wt%, preferably 1.0 wt% ~ 10.0wt%.

17. in accordance with the method for claim 1, it is characterised in that: the temperature of described immersion is 30 DEG C ~ 120 DEG C, preferably 45 DEG C ~ 100 DEG C, and soak time is 4h ~ 20h, preferably 8h ~ 15h；The described temperature being dried is 60 DEG C ~ 200 DEG C, preferably 80 DEG C ~ 150 DEG C, drying time 1h ~ 20h, preferably 3h ~ 15h.

18. in accordance with the method for claim 1, it is characterised in that: it is being dried the step also including continuing to carry out heat treatment in vacuum environment or inert atmosphere between roasting.

19. in accordance with the method for claim 18, it is characterized in that: described heat treatment is under inert gas atmosphere, impregnated catalyst is processed in two stages, the control condition of first stage: temperature is 250 DEG C ~ 350 DEG C, being 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 450 DEG C ~ 500 DEG C, and the time is 2h ~ 4h.

20. in accordance with the method for claim 1, it is characterised in that: the condition of described roasting is: contacted with oxygen-containing gas by described catalyst, and temperature is 300 DEG C ~ 600 DEG C, preferably 350 DEG C ~ 550 DEG C, and the time is 1.0h ~ 10h, preferably 2.0h ~ 8.0h.