CN106179486B

CN106179486B - A kind of regeneration method containing noble metal and EUO type molecular sieve catalyst

Info

Publication number: CN106179486B
Application number: CN201510210306.4A
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: 2018-06-19
Anticipated expiration: 2035-04-29
Also published as: CN106179486A

Abstract

The invention discloses a kind of regeneration methods containing noble metal and EUO type molecular sieve catalyst.The catalyst includes EUO type molecular sieve and the VIIIth race's noble metal component, regenerative process include：First deactivation catalyst of carbon deposit is handled, then compounds containing sodium is loaded and containing lanthanum compound using infusion process with organic solvent, the atomic ratio for impregnating metal platinum in the lanthanum and catalyst loaded on rear catalyst is 6:1~1:1, the atomic ratio of metal platinum is 10 in the sodium and catalyst that load on catalyst:1~1:1, the first roasting is carried out under oxygen-containing gas effect, reduction treatment is carried out after the completion of first roasting, the second roasting is carried out under oxygen-containing gas effect again, the maximum temperature of first roasting process is not higher than 500 DEG C, second calcination process is impregnated through aqueous ammonium nitrate solution after completing, is washed, most afterwards through being dried to obtain regenerated catalyst.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

A kind of regeneration method containing noble metal and EUO type molecular sieve catalyst

Technical field

The present invention relates to a kind of regeneration methods containing noble metal and EUO type molecular sieve catalyst.More specifically, it is of the invention It is related to a kind of regeneration method of catalyst, which tautomerizes to the process of paraxylene for ortho-xylene and meta-xylene, It is related to C simultaneously₈The conversion of ethylbenzene in aromatic hydrocarbons.

Background technology

In the production of petrochemical industry, the C that is obtained from techniques such as the vapor thermal crackings of catalytic reforming or hydrocarbon ils₈In aromatic hydrocarbons Contain dimethylbenzene（Including paraxylene, meta-xylene and ortho-xylene）And ethylbenzene.To meet synthetic fibers to paraxylene It needs, ethylbenzene is mostly generally isolated using appropriate method, and the means for passing through adsorbing separation and isomerization increase paraxylene Content.But since the boiling point of ethylbenzene and dimethylbenzene is very close, adding for ethylbenzene is directly separated with highly efficient distilling or adsorbing separation Work is costly, economically uneconomical, so mostly converting the ethylbenzene into dimethylbenzene or benzene using chemical reaction in recent years.

In order to which ethylbenzene conversion and the reaction of xylene isomerization is made to complete simultaneously, with the solid acid catalysis containing hydrogenation component The method that agent converts the ethylbenzene into benzene and ethane and xylene isomerization is turned to thermodynamical equilibrium mixture increasingly draws attention. During ethylbenzene hydro-dealkylation generates benzene and ethane, the conversion of ethylbenzene is hardly restricted by thermodynamical equilibrium, conversion ratio compared with It is high；Benzene differs larger with xylene boiling point simultaneously, can be detached with fractionation.The benzene isolated is in synthetic fibers and synthetic resin It is also highly advantageous to use value in industry.In this method for transformation, the activity of catalyst is in diformazan by the paraxylene in product Content and conversion of ethylbenzene in benzene are weighed, and the selectivity of catalyst is then the selection by dimethylbenzene yield and ethylbenzene generation benzene Property is weighed.

So will the bottom product low to paraxylene content further upgraded, method is to be carried out isomerization, In isomerization, at least part ethylbenzene experience hydrogenolysis and generate benzene and ethane, and a part of ortho-xylene and two Toluene isomerization generates a kind of mixture, which again can be close to the equilibrium concentration of o-, m- and p- dimethylbenzene.And the prior art The zeolite catalyst of the general one or more metals of multipurpose load, carrier are mostly used aluminium oxide, and zeolite be mostly used modenite or ZSM series zeolites.

And activity can continuously decrease the catalyst that oil-refining chemical process uses in use, i.e. catalyst inactivation, return Reason of receiving 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） And sintering deactivation（Cause the change of catalyst crystalline phases）Deng.The main reason for industrial hydrogenation catalyst inactivation is coke generation and gold Belong to block, active metal component migration or aggregation, the variation of phase composition, number of active center is reduced, carrier is sintered, zeolite structured collapses Sunken and collapse etc..The decaying catalyst for caused by carbon deposit can restore its activity with regeneration method, and for metal deposit dirt Decaying catalyst caused by dye, it is impossible to which regeneration is 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 area are all There is 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, the isomerization of C-8 aromatics that this method is not suitable for using noble metal and molecular screen material as active component are catalyzed In agent.

The active metal that isomerization of C-8 aromatics catalyst uses is generally noble metal, and carrier generally uses EUO type molecule Sieve, is a kind of catalyst containing noble metal and molecular sieve simultaneously.The catalyst has suitable acid centre and hydrogenation activity, The reactivity and selectivity that can make catalyst greatly improve, and are in particular in that C8 aronmatic yield and conversion of ethylbenzene obtain To raising.

Isomerization of C-8 aromatics catalyst wraps the main reason for activity decline in the reaction as a kind of molecular sieve catalyst Include the following：（1）Carbon deposit covers the active sites of catalyst or plugs the duct of catalyst on catalyst；（2）Raw material In the compounds such as sulphur nitrogen make catalyst poisoning；（3）The aggregation of metal or the destruction of carrier structure；（4）In raw material metal or The nonmetallic deposition of person, such as silicon, arsenic, iron etc..Since isomerization of C-8 aromatics catalyst is that one kind contains molecular sieve and noble metal Catalyst because molecular sieve is a kind of crystallization of metastable state, under certain condition（Such as high temperature, illumination, long-time etc.）Hold very much Easily lead to crystallization of molecular sieves structural damage, moreover it is possible to cell channels be made to cave in, block duct, original catalyst can be lost Type reactivity worth is selected, and is easy to cause the aggregation of metal, once accumulation of metal, it is impossible to gold is carried out as reforming catalyst The chlorination update of category（At high temperature, chlorine and vapor are very big to the destruction of molecular sieve structure）Even if added after making charcoal using organic The conventional methods such as agent is added to handle, it is also difficult to it be made to be disperseed well again.It can be seen that conventional catalyst high temperature is made charcoal again Generation method will seriously destroy the performance of the catalyst.So general noble metal catalyst（Such as reforming catalyst）Regeneration side Method is not suitable for the regeneration of isomerization dewaxing catalyst, in entire regenerative process, it is necessary to the temperature of stringent control catalyst particle surface Height is spent, and ensures that oxidation is thorough, specially requires in catalyst regeneration process strictly control regeneration temperature and oxygen content thus. So isomerization of C-8 aromatics catalyst regeneration key is to find a carbon deposit that can be as possible on Removal of catalyst, while again It 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 molecular sieve catalyst is encountered in high temperature regeneration, particularly aggregation occurs for metal platinum, molecular sieve structure is broken Bad the problems such as.

Invention content

In order to overcome shortcoming of the prior art, urged the present invention provides one kind containing noble metal and EUO type molecular sieve The regeneration method of agent is particularly suitable for the catalyst recovery process containing EUO type molecular sieve and the VIIIth race's noble metal component, especially It is the regeneration method of isomerization of C-8 aromatics catalyst.Regeneration methods of the invention is not only able to effectively remove product at low temperature Charcoal ensures that catalyst pore structure is not destroyed, but also can assemble to avoid noble metal, noble metal dispersion can be made good, after regeneration The reactivity worth of catalyst can be restored to fresh catalyst level.

The present invention provides a kind of regeneration method containing noble metal and EUO type molecular sieve catalyst, which includes EUO type Molecular sieve and the VIIIth race's noble metal component, regenerative process include：Deactivation catalyst of carbon deposit first is handled with organic solvent, then using leaching Stain method loads compounds containing sodium and containing lanthanum compound, and the atomic ratio of metal platinum is 6 in the addition and catalyst of lanthanum:1~1:1, sodium Addition and catalyst in metal platinum atomic ratio be 10:1~1:1, the first roasting of progress under oxygen-containing gas effect, first Reduction treatment is carried out after the completion of roasting, then the second roasting, the maximum temperature of the first roasting process are carried out under oxygen-containing gas effect Not higher than 500 DEG C, through aqueous slkali soaking, washing after the completion of the second calcination process, most afterwards through being dried to obtain regenerated catalyst.

Involved EUO type molecular sieve is one or more of EU-1, ZSM-50 and TPZ-3 in the method for the present invention. EU-1 molecular sieves are preferably comprised, noble metal component is selected from group VIII metal platinum.Refractory porous inorganic oxide can also be contained, than It is one or more in such as aluminium oxide, silica, titanium oxide, zirconium oxide.On the basis of the weight of catalyst, EUO type molecule The content of sieve is 1.0wt% ~ 60wt%, preferably 2.0wt% ~ 50wt%, the content of noble metal is 0.05wt% ~ 5.0wt%, and refractory is more Mesoporous inorganic oxide is surplus.

In the method for the present invention, decaying catalyst is first handled with organic solvent, used in organic solvent can be general One or more of benzene, ethyl alcohol, gasoline, kerosene can be used, leaching may be used in the method for organic solvent processing decaying catalyst The common methods such as bubble, distillation.The volume ratio of organic solvent and decaying catalyst is 8:1~1:1.

In the method for the present invention, when infusion process load is containing lanthanum compound and compounds containing sodium, a step infusion process may be used, Step impregnation method, preferably single-steeping method can also be used.When using a step infusion process, the maceration extract used in infusion process is adopted With dissolved with the aqueous solution containing lanthanum compound and compounds containing sodium, wherein, can be lanthanum nitrate, lanthanum acetate, sulphur containing lanthanum compound One or more in sour lanthanum, the concentration containing lanthanum compound is calculated as 1.0wt% ~ 10wt% with lanthanum element, and compounds containing sodium is chlorination One or more in sodium, sodium sulphate, sodium nitrate, sodium carbonate, the concentration of compounds containing sodium is calculated as 5.0 wt% ~ 20 with sodium element wt%。

When using step impregnation method, conventional step impregnation method may be used and loaded containing the water-soluble of lanthanum compound Liquid and compounds containing sodium can first load the aqueous solution containing lanthanum compound, can also first load compounds containing sodium.Step impregnation Maceration extract includes two kinds of solution of aqueous solution of aqueous solution and compounds containing sodium containing lanthanum compound, the aqueous solution containing lanthanum compound Concentration is calculated as 1.0wt% ~ 10wt% with lanthanum element, and the concentration of the aqueous solution of compounds containing sodium is calculated as 5.0 wt% ~ 20 with sodium element wt%。

After infusion process load is containing lanthanum compound and compounds containing sodium, the original of platinum wherein in the load capacity of lanthanum and decaying catalyst Sub- ratio is 4:1~2:1, the atomic ratio of platinum is 8 in the load capacity and decaying catalyst of sodium:1~3:1.

In the method for the present invention, the roasting condition of the first roasting and the second roasting can be the same or different.Described One roasting condition be：The catalyst is contacted with oxygen-containing gas, 300 DEG C ~ 450 DEG C of temperature, preferably 320 DEG C ~ 420 DEG C, Time of contact is 1.0h ~ 10h, preferably 2.0h ~ 8.0h.The condition of described second roasting is：By the catalyst with it is oxygen-containing Gas contact, 300 DEG C ~ 600 DEG C of temperature, preferably 350 DEG C ~ 550 DEG C, time of contact be 1.0h ~ 10h, preferably 2.0h ~ 8.0h.Oxygen content can be 0.2v% ~ 25v%, preferably 0.5v% ~ 10v% in oxygen-containing gas.

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 for 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, a concentration of 15wt% ~ 55wt% of the aqueous ammonium nitrate solution, preferably 20wt% ~ 50wt%, tool Body operating condition is：20 DEG C ~ 90 DEG C of temperature, the time be 1.0h ~ 8.0h, preferable temperature be 30 DEG C ~ 80 DEG C, the time for 2.0h ~ 6.0h.Catalyst after washing is again through being dried, and drying temperature can be 60 DEG C ~ 200 DEG C, preferably 70 DEG C ~ 160 DEG C, More preferably 80 DEG C ~ 120 DEG C, drying time can be 1.0h ~ 20h, more preferably preferably 3.0h ~ 15h, 5.0h ~ 10h.

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）The first calcination temperature is strictly controlled during roasting, is controlled at 500 DEG C hereinafter, being not only able in low temperature It is lower effectively to remove carbon deposition removal, ensure that catalyst pore structure is not destroyed, and can effectively avoid the process due to carbon in burning It is middle to release big calorimetric, cause burning carbon temperature excessively high, so as to cause the aggregation of active metal and the performance of catalyst by larger The problem of influence.And 600 DEG C of the temperature of second of roasting is controlled hereinafter, not only can be with the residual after deep removal for the first time roasting Part carbon can release small part heat, so as to destroy catalyst pores to avoid residual fraction carbon after roasting for the first time in combustion process Structure and the problem of cause the aggregation of active metal.

（3）Loaded on the catalyst after being handled through organic solvent it is a certain amount of containing lanthanum compound and compounds containing sodium, And the first roasting is carried out at a lower temperature.Lanthanum forms Pt-Na-La with the platinum on sodium and decaying catalyst and answers in the process Polymerisable compounds are disperseed, and are roasted using reduction treatment and second, can more effectively avoid the aggregation of noble metal, are improved expensive The dispersion of metal platinum, while EUO type molecular sieve structural damage is avoided, the catalyst after second of roasting is molten using ammonium nitrate The mode of liquid washing removes sodium, and the catalyst after the regeneration obtained in this way not only can guarantee that catalyst pore structure is not destroyed, gold Belonging to Pt has preferably dispersion, and can be also prevented from metal La and Pt in the process and be lost in, since the collaboration of La-Pt is made With can improve the hydrogenation/dehydrogenation reactivity of catalyst, make the performance recovery of catalyst to fresh catalyst level.

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 ~ 12h of temperature, feedstock oil master used in evaluation Property is wanted to be shown in Table 1.

1 feedstock property of table（Volumn concentration）

Ethylbenzene	7.9%
		Paraxylene	0.1%
Meta-xylene	70.2%
		Ortho-xylene	21.8%

The present invention relates to FW-1 decaying catalysts be fresh catalyst be certain commercial xylene isomerization device industry Deactivator after operating.The physico-chemical property of FW-1 decaying catalysts is as follows：Specific surface area is 152m²/ g, Kong Rongwei 0.30mL/g, Pt content 0.45wt%, C content are 7.8 wt %.The composition and property that fresh dose of FW-1 are as follows：Specific surface area is 275m²/ g, hole Hold for 0.38mL/g, the content of Pt contents 0.50wt%, EU-1 molecular sieve is 6.5wt%.

The physico-chemical property of FW-2 decaying catalysts of the present invention is as follows：Specific surface area is 143 m²/ g, Kong Rongwei 0.43 wt% of 0.28 mL/g, Pt content, C content are 10.38 wt %.The composition and property that fresh dose of FW-2 are as follows：Specific surface Product is 280 m²The content of/g, Kong Rongwei 0.38mL/g, Pt content 0.50wt%, TPZ-3 molecular sieve is 6.0wt%.

The physico-chemical property of FW-3 decaying catalysts of the present invention is as follows：Specific surface area is 150m²/ g, Kong Rongwei 0.44 wt% of 0.26mL/g, Pt content, C content are 9.38 wt %.The composition and property that fresh dose of FW-3 are as follows：Specific surface area For 285m²The content of/g, Kong Rongwei 0.37mL/g, Pt content 0.50wt%, ZSM-50 molecular sieve is 7.5wt%.

Wherein FW-2 and FW2-3 is laboratory rapid deactivation agent

Embodiment 1

The preparation of catalyst E-1 of the present invention.

1450mL organic solutions are added in the flask of 2000mL（Wherein ethyl alcohol and benzene volume volume ratio are 2:1）, to work 200mL xylene isomerization decaying catalyst FW-1 processing after industry operating, it is Ca-1 to distill the catalyst number after 2h.

Take 27.8g lanthanum nitrates（Lanthanum content 3.0wt%）, 2.12g sodium nitrate（Na contents 10.0wt%）Prepare the leaching containing lanthanum/sodium Stain liquid takes Ca-1 catalyst 100g to carry out saturation dipping, and the atomic ratio that La and Pt, Na and Pt is made is respectively 3:1 and 4:1 contains The catalyst sample of lanthanum/sodium, then the heating rate with 3 DEG C/min are warming up to 350 DEG C of constant temperature 5h.Gained catalyst number is Ea- 1。

Above-mentioned catalyst Ea-1 carries out the first calcination process under air atmosphere, and actual conditions are：With the heating of 3 DEG C/min Speed is warming up to 360 DEG C of constant temperature 5h.First calcined catalyst is subjected to reduction treatment under an atmosphere of hydrogen, actual conditions are： Hydrogen Vapor Pressure is 3.5MPa, and reduction temperature is 430 DEG C, recovery time 6h；By the catalyst after reduction treatment in air atmosphere Lower to carry out the second roasting, actual conditions are：With the heating rate of 3 DEG C/min, it is warming up to 450 DEG C of constant temperature 3h.Gained catalyst is compiled Number be Ea-2.

Take 35wt%（With NH₄NO₃Meter）Aqueous ammonium nitrate solution 300g adds in the above-mentioned catalyst Ea-2 of 100g, and temperature is at 50 DEG C Lower washing 4.0h, then through 120 DEG C of dry 10h, catalyst E-1 of the present invention is obtained, specific treatment conditions are shown in Table 2, and reaction result is shown in Table 3.

Embodiment 2

The preparation of catalyst E-2 of the present invention

Take 17.4g lanthanum acetates（Lanthanum content 8.0wt%）Maceration extract is configured to, Ca-1 catalyst is prepared according to 1 method of embodiment 100g carries out supersaturated dipping, and the atomic ratio that La and Pt is made is 5:1 sample containing lanthanum catalyst, after drying and roasting, Take 1.59g sodium sulphate（Na contents 10.0wt%）Maceration extract is configured to, the above-mentioned catalyst containing lanthanum is taken to carry out saturation dipping, is made The atomic ratio of Sn and Pt is 3:1 catalyst sample containing lanthanum/sodium, then the heating rate with 3 DEG C/min are warming up to 420 DEG C of perseverances Warm 4h.Gained catalyst number is Eb-1.

Above-mentioned catalyst Eb-1 carries out the first roasting under air atmosphere, and actual conditions are：With the heating speed of 3 DEG C/min Degree, is warming up to 450 DEG C of constant temperature 4h.First calcined catalyst is subjected to reduction treatment under an atmosphere of hydrogen, actual conditions are：Hydrogen Atmospheric pressure is 4.5MPa, and reduction temperature is 480 DEG C, recovery time 5h；By the catalyst after reduction treatment under air atmosphere Second calcination process, actual conditions are：With the heating rate of 3 DEG C/min, it is warming up to 500 DEG C of constant temperature 3h, gained catalyst number For Eb-2.

Take 25wt%（With NH₄NO₃Meter）Aqueous ammonium nitrate solution 300g adds in the above-mentioned catalyst Ea-2 of 100g, and temperature is at 70 DEG C Lower washing 2.5h, then through 120 DEG C of dry 10h, catalyst E-1 of the present invention is obtained, specific treatment conditions are 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）, it is right Decaying catalyst FW-1 processing after 200mL industrial operations, it is Cb-1 to distill the catalyst number after 2h.

Take 83.4g lanthanum sulfates（Lanthanum content 2.0wt%）, 2.12g sodium carbonate（Na contents 20.0wt%）Prepare the leaching containing lanthanum/sodium Stain liquid takes Cb-1 catalyst 100g to carry out saturation dipping, and the atomic ratio that La and Pt, Sn and Pt is made is respectively 6:1 and 8:1 contains The catalyst sample of lanthanum/sodium, then the heating rate with 3 DEG C/min are warming up to 350 DEG C of constant temperature 5h.Gained catalyst number is Ec- 1。

Above-mentioned catalyst Ec-1 carries out the first roasting under air atmosphere, and actual conditions are：With the heating speed of 3 DEG C/min Degree, is warming up to 350 DEG C of constant temperature 5h.First calcined catalyst is subjected to reduction treatment under an atmosphere of hydrogen, actual conditions are：Hydrogen Atmospheric pressure is 2.5MPa, and reduction temperature is 450 DEG C, recovery time 7h；By treated, catalyst carries out under air atmosphere Second calcination process, actual conditions are：With the heating rate of 3 DEG C/min, it is warming up to 350 DEG C of constant temperature 3h.Gained catalyst is numbered For Ec-2.

Take 15wt%（In terms of NaOH）Sodium hydrate aqueous solution 300g adds in the above-mentioned catalyst Ec-2 of 100g, impregnates at room temperature 10h, then through 120 DEG C of dry 10h, catalyst E-3 of the present invention is obtained, specific treatment conditions are shown in Table 2, and reaction result is shown in Table 3.

Take 45wt%（With NH₄NO₃Meter）Aqueous ammonium nitrate solution 300g adds in the above-mentioned catalyst Ea-2 of 100g, and temperature is at 20 DEG C Lower washing 6.0h, then through 120 DEG C of dry 10h, catalyst E-1 of the present invention is obtained, specific treatment conditions are 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

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, lanthanum and sodium solution and roasting are different with the temperature of reduction, and the catalyst E-4 ~ E-6 of the present invention prepared is specific to handle Condition 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, and the difference lies in catalyst to use containing lanthanum compound, number C-1, Its 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, the difference lies in catalyst without using compounds containing sodium, number C- 2, specific treatment conditions are 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, although the difference lies in catalyst by being handled containing lanthanum/sodium solution, But only roasted by a calcination process without reduction treatment and second, number C-3, specific treatment conditions are shown in Table 2, reaction result is shown in Table 3.

Comparative example 4

It is prepared by comparative catalyst C-4 of the present invention.

The preparation method is the same as that of Example 1 for catalyst, although being handled the difference lies in catalyst by lanthanum/sodium solution, again By the first roasting, reduction treatment and the second roasting, but without aqueous slkali soaking, carrying out washing treatment, number C-4, tool Body treatment conditions are 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	Hydrogen Vapor Pressure, MPa	The reduction temperature time	Second roasting	Concentration of ammonium nitrate solution, wt%
					E-1	3.5	430℃×6h	450℃×3h	35
E-2	4.5	480℃×5h	500℃×3h	25
					E-3	2.5	450℃×7h	350℃×3h	45
E-4^③	3.2	400℃×5h	510℃×4h	20
					E-5	3.8	410℃×5h	510℃×2h	50
E-6^④	4.0	270℃×10h	500℃×5h	35
					C-1	3.5	410℃×6h	450℃×3h	35
C-2	3.5	410℃×6h	450℃×3h	--
					C-3	--	--	--	35
C-4	3.5	410℃×6h	450℃×3h	--

Note：Ethyl alcohol/benzene, 2. gasoline/kerosene, 3. FW-2 decaying catalysts, 4. FW-3 decaying catalysts

The evaluation result of 3 catalyst of table

Example number	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6
							PX/ ∑s X, %	23.5	23.3	23.5	23.0	23.1	23.5
Xylene loss, %	2.6	2.7	2.5	2.3	2.6	2.7
							Conversion of ethylbenzene, %	33	32	31	33	32	31

Continued 3

Embodiment or comparison number	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Fresh dose of FW-1	FW-1 deactivators
							PX/ ∑s X, %	20.8	22.6	21.1	20.3	23.5	15.7
Xylene loss, %	4.0	3.3	3.7	3.5	2.5	5.7
							Conversion of ethylbenzene, %	19	28	23	21	32	10.6

Note：PX represents paraxylene, and ∑ X represents dimethylbenzene total amount

It can be seen from the result of table 3 compared with comparative catalyst, the close balance of paraxylene content, conversion of ethylbenzene Improve more than 20wt%, xylene loss reduces 30wt% or so, and reactivity worth is substantially better than comparative catalyst, close to it is new Fresh catalyst.

Claims

1. a kind of regeneration method containing noble metal and EUO type molecular sieve catalyst, which includes EUO type molecular sieve and the VIIIth Race's noble metal component, which is characterized in that regenerative process includes：Deactivation catalyst of carbon deposit first is handled with organic solvent, then using leaching Stain method loads compounds containing sodium and containing lanthanum compound, impregnates the atomic ratio of metal platinum in the lanthanum and catalyst loaded on rear catalyst It is 6:1~1:1, the atomic ratio of metal platinum is 10 in the sodium and catalyst that load on catalyst:1~1:1, under oxygen-containing gas effect The first roasting is carried out, reduction treatment is carried out after the completion of the first roasting, then the second roasting is carried out under oxygen-containing gas effect, the first roasting The maximum temperature of burning process is not higher than 500 DEG C, and the second calcination process is impregnated through aqueous ammonium nitrate solution after completing, washed, and is most passed through afterwards It is dried to obtain regenerated catalyst.

2. according to the method for claim 1, it is characterised in that：In the catalyst, noble metal component is platinum, EUO type Molecular sieve is one or more of EU-1, ZSM-50 and TPZ-3.

3. according to the method for claim 1, it is characterised in that：In the catalyst, EUO type molecular sieve, your gold contained Belong to platinum and refractory porous inorganic oxide, on the basis of the weight of catalyst, the content of molecular sieve is 1.0wt% ~ 60wt%, your gold The content of category is the wt% of 0.01 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 2.0wt%~50wt%。

5. according to the method for claim 1, it is characterised in that：The catalyst is isomerization of C-8 aromatics catalyst.

6. according to the method for claim 1, it is characterised in that：After infusion process load is containing lanthanum compound and compounds containing sodium, The atomic ratio of platinum is 4 in the lanthanum and decaying catalyst that are loaded on catalyst:1~2:1, the sodium loaded on catalyst is catalyzed with inactivation The atomic ratio of platinum is 8 in agent:1~3:1.

7. according to the method for claim 1, it is characterised in that：Decaying catalyst is first handled with organic solvent, wherein Organic solvent used is one or more in ethyl alcohol, benzene, gasoline and kerosene.

8. according to the method for claim 1, it is characterised in that：Decaying catalyst is first handled with organic solvent, wherein The method of organic solvent processing decaying catalyst is using the method impregnated or distilled.

9. according to the method for claim 1, it is characterised in that：The volume ratio of organic solvent and decaying catalyst is 8:1~1: 1。

10. according to the method for claim 1, it is characterised in that：Infusion process load is containing lanthanum compound and compounds containing sodium Method is a step infusion process, and maceration extract is used dissolved with the aqueous solution containing lanthanum compound and compounds containing sodium, wherein, chemical combination containing lanthanum The concentration of object is calculated as 1.0wt% ~ 10wt% with lanthanum element, and the concentration of compounds containing sodium is calculated as 5.0wt% ~ 20wt% with sodium element.

11. according to the method for claim 1, it is characterised in that：Infusion process load is containing lanthanum compound and compounds containing sodium Method is step impregnation method, and maceration extract includes the aqueous solution of aqueous solution and compounds containing sodium containing lanthanum compound, containing lanthanum compound The concentration of aqueous solution 1.0wt% ~ 10wt% is calculated as with lanthanum element, the concentration of the aqueous solution of compounds containing sodium is calculated as with sodium element 5.0wt%~20wt%。

12. according to the method described in claim 10 or 11, it is characterised in that：Lanthanum compound is lanthanum nitrate, lanthanum acetate, lanthanum sulfate In it is one or more, compounds containing sodium is sodium chloride, sodium sulphate, sodium nitrate, one or more in sodium carbonate.

13. according to the method for claim 1, it is characterised in that：The condition of described first roasting is：By the catalyst It is contacted with oxygen-containing gas, temperature is 300 DEG C ~ 450 DEG C, and the time is 1.0h ~ 10h.

14. according to the method for claim 13, it is characterised in that：The condition of described first roasting is：By the catalysis Agent is contacted with oxygen-containing gas, and temperature is 320 DEG C ~ 420 DEG C, and the time is 2.0h ~ 8.0h.

15. according to the method for claim 1, it is characterised in that：The condition of described second roasting is：By the catalyst It is contacted with oxygen-containing gas, temperature is 300 DEG C ~ 600 DEG C, and the time is 1.0h ~ 10h.

16. according to the method for claim 15, it is characterised in that：The condition of described second roasting is：By the catalysis Agent is contacted with oxygen-containing gas, and temperature is 350 DEG C ~ 550 DEG C, and the time is 2.0h ~ 8.0h.

17. according to the method described in any one in claim 1,13-16, it is characterised in that：Oxygen in the oxygen-containing gas Content is 0.2v% ~ 25v%.

18. according to the method for claim 17, it is characterised in that：In the oxygen-containing gas oxygen content for 0.5v% ~ 10v%。

19. 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 1.0h ~ 15h, and Hydrogen Vapor Pressure is 0.5MPa ~ 6.0MPa.

20. according to the method for claim 19, 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, and the time is 5.0h ~ 10h, and Hydrogen Vapor Pressure is 1.0MPa ~ 4.0MPa.

21. according to the method for claim 1, it is characterised in that：A concentration of 15%wt ~ 55 of the aqueous ammonium nitrate solution wt %。

22. according to the method for claim 21, it is characterised in that：A concentration of 20wt% of the aqueous ammonium nitrate solution ~ 50wt%。

23. according to the method for claim 1, it is characterised in that：The wash temperature is 20 DEG C ~ 100 DEG C, wash time For 1.0h ~ 8.0h.

24. according to the method for claim 23, it is characterised in that：The wash temperature is 40 DEG C ~ 90 DEG C, wash time For 2.0h ~ 6.0h.

25. according to the method for claim 1, it is characterised in that：The condition of the drying is as follows：Temperature is 60 ~ 200 DEG C, the time is 1.0 ~ 20h.

26. according to the method for claim 25, it is characterised in that：The condition of the drying is as follows：Temperature is 70 ~ 160 DEG C, the time is 3.0 ~ 15h.

27. according to the method for claim 25, it is characterised in that：The condition of the drying is as follows：Temperature is 80 ~ 120 DEG C, the time is 5.0 ~ 10h.