CN101992131A - Method for regenerating hydrogenation catalyst, regenerated hydrogenation catalyst and application thereof - Google Patents
Method for regenerating hydrogenation catalyst, regenerated hydrogenation catalyst and application thereof Download PDFInfo
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Abstract
The invention discloses a method for regenerating a hydrogenation catalyst, the regenerated hydrogenation catalyst and application thereof. Based on the total amount of components which cannot be burnt in the catalyst, the delta P value of the regenerated hydrogenation catalyst is 0.1 to 4.5 weight percent. The preparation method comprises the following steps of: (1) under the reaction condition of regenerated charcoaling of the hydrogenation catalyst, making a catalyst to be regenerated contact an oxygen-containing gas; (2) making the catalyst charcoaled in the step (1) contact the solution of a phosphorus compound; and (3) drying the catalyst contacted in the step (2). Compared with the prior art, the regenerated catalyst provided by the invention has obviously improved activity.
Description
Technical field
The present invention relates to a kind of renovation process, regeneration hydrogenation catalyst and application thereof of hydrogenation catalyst.
Background technology
Under hydrogenation conditions, to cause inactivation be a kind of general phenomenon to hydrogenation catalyst (comprising Hydrobon catalyst, hydrotreating catalyst, hydrocracking catalyst etc.) because of carbon deposit in use takes place.Because industrial hydrogenation catalyst need use 2 above cycles usually, therefore need be to processing of regenerating of the hydrotreating catalyst of inactivation, to recover most of activity of catalyst, can reusable purpose thereby reach.
CN1125474C discloses a kind of process for regenerating hydrocatalyst, this method is with after the deactivated hydrogenation catalyst preheating, the low-temperature zone of passing through 300 ℃～350 ℃ successively heated 1～7 hour, the high temperature section heating of 400 ℃～500 ℃ middle-temperature section heating 1～7 hour and 550 ℃～600 ℃ 1～10 hour obtains regenerated catalyst again after cooling off naturally.
US6239054B1 discloses a kind of chelating agent that adopts and has handled decaying catalyst to improve active method, this method comprises with the decaying catalyst after ethylenediamine tetra-acetic acid two ammoniums (EDTA) the dipping industry regeneration, in 60 ℃ of following closed containers, wore out 4 days afterwards, carry out drying and roasting at last.In the method, chelating agent is removed from catalyst in roasting process.
US6635596 has reported the renovation process that a kind of additive is catalyst based, comprise contacting with oxygen-containing gas being no more than under 500 ℃ the temperature used additive is catalyst based that described renovation process comprises low temperature step (100 ℃～370 ℃) and high-temperature step (300 ℃～500 ℃).Described additive is selected from compound or derivatives thereof that contains at least two oxygen atoms and 2～10 carbon atoms or the compound that contains at least one covalent bond nitrogen-atoms and at least one carbonyl.
US7087546B2 has reported regeneration and the method for activation recovering that a kind of additive is catalyst based, this method comprises used old catalyst is contacted with oxygen-containing gas being no more than under 500 ℃ the temperature, contact with organic additive more afterwards and organic additive is introduced in the catalyst, if necessary then under 50% additive retains in situation in the catalyst, carry out drying.Wherein mention in the case of necessary, the carbon content of regenerative agent is controlled at below 3%, and baking temperature is comparatively favourable below 200 ℃ usually.Described organic additive is selected from compound or its ethers that contains at least two oxygen atoms and 2～10 carbon atoms or the compound that contains at least one covalent bond nitrogen-atoms and at least one carbonyl.
Chinese patent CN1921942A has reported a kind of method of recovering the spent hydroprocessing catalyst activity, comprise the processing of making charcoal of the spent hydroprocessing catalyst of carbon distribution, obtain the middle catalyst that carbon content is reduced to 0.5～2.5 total amount %, this centre catalyst is contacted and burin-in process with nitrogenous chelating agent solution, wherein ageing treatment time was above 10 hours, last drying is handled the catalyst that obtains regenerating, and wherein introduces being retained in more than 50% in the dried catalyst of chelating dosage.
Catalyst nickeliferous and/or cobalt, molybdenum and/or tungsten hydrogenation metal component is common hydrogenation catalyst.For improving activity and stability, this class catalyst must be converted into sulfide with the hydrogenation metal component through presulfurization before use usually.Therefore, in the catalyst regeneration process, when burning, be attended by the oxidation reaction of sulfide.Its typical reaction is as follows:
Under high-temperature oxygen-enriched situation, part SO
2Can change into SO
3The water reaction that these sulphur-containing substances run in the regeneration atmosphere generates sulfurous acid and sulfuric acid, makes the performance of regeneration rear catalyst become bad easily.For example, make that contained framework of molecular sieve subsides in the hydrocracking catalyst, metal ion transport changes original reactive metal phase, and then causes the irreversible decline of catalyst performance or completely lose.Be to reduce the infringement of sulfide, can and take off charcoal and in two combustion chambers, carry out (referring to the 26th page of " petroleum refining collected translation " the 3rd phase in 1986) respectively desulfurization to catalyst activity.
CN1782030A discloses a kind of process for regenerating hydrocatalyst, and this method comprises: 1) the graininess alkaline matter is mixed with the inactivation hydrogenation catalyst, its weight mixing ratio is 5: 95～50: 50; 2) under the oxidation regeneration reaction condition, the graininess alkaline matter is contacted with oxygen-containing gas with the mixture of inactivation hydrogenation catalyst; 3) separation regeneration hydrogenation catalyst.Claim the active high of the employing regenerated catalyst that this method obtains, can make regeneration discharge SO in the tail gas simultaneously
2Content obviously reduce.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of new, active hydrogenation catalyst, the method that obtains this catalyst and this Application of Catalyst of obviously improving or improving that obtains through regeneration.
The invention provides a kind of renovation process of hydrogenation catalyst, comprising:
(1) under the reaction condition that hydrogenation catalyst regeneration is made charcoal, will treat that regenerated catalyst contacts with oxygen-containing gas;
(2) will contact with the solution that contains phosphorus-containing compound through the catalyst after make charcoal step (1);
(3) will be through the catalyst drying of step (2) contact, the catalyst that obtains regenerating;
Wherein, be benchmark in oxide and with total amount that can not the burn off component in the catalyst, it is 0.1～5 weight % that the contact of described step (2) makes regenerated catalyst Δ P value; The increment of phosphorus in the Δ P value representative regeneration rear catalyst, Δ P=P
1%-P
0%, wherein, P
1The content of phosphorus in the % representative regeneration rear catalyst, P
0The content of phosphorus in the % representative regeneration procatalyst.
The invention provides a kind of regeneration hydrogenation catalyst, is benchmark in oxide and with total amount that can not the burn off component in the catalyst, and the Δ P value of the hydrogenation catalyst of described regeneration is 0.1～5 weight %; The increment of phosphorus in the Δ P value representative regeneration rear catalyst, Δ P=P
1%-P
0%, wherein, P
1The content of phosphorus in the % representative regeneration rear catalyst, P
0The content of phosphorus in the % representative regeneration procatalyst.
The present invention also provides a kind of hydrogenation method for hydrocarbon oils, is included under the hydrogenation conditions hydrocarbon ils is contacted with catalyst, it is characterized in that, described catalyst is aforementioned regeneration hydrogenation catalyst provided by the invention.
Compared with prior art, the activity of regenerated catalyst provided by the invention is significantly improved and enhanced.For example, with the activity of the desulphurizing activated sign regenerated catalyst of relative volume, and be 100% with the activity of such catalysts of Comparative Examples method regeneration, then compare with the Comparative Examples method, the invention provides regenerated catalyst can reach more than 130%.
The specific embodiment
According to method provided by the invention, wherein the described hydrogenation catalyst of step (1) the regeneration reaction condition of making charcoal is the habitual condition of hydrogenation class catalyst coke-burning regeneration.Comprise in the hydrogenation catalyst introducing catalyst regeneration device of to wait to regenerate, heat and introduce oxygen-containing gas.Wherein, described coke-burning regeneration device can be tunnel cave, rotary kiln, moving bed, batch-type furnace and tube furnace, described oxygen-containing gas can be the gaseous mixture of oxygen or air and any one inert gas, oxygen content in the gaseous mixture is preferably 0.5～40 volume %, and inert gas can be selected from one or more in nitrogen, argon gas, helium, carbon dioxide, flue gas and the water vapour.Charcoal temperature preferably is no more than 500 ℃, more preferably 320 ℃～480 ℃, is more preferably 350 ℃～430 ℃.In practical operation, look the difference of charcoal, sulfur content or physico-chemical property in the hydrogenation catalyst of waiting to regenerate, various operating conditions during catalyst regeneration, can be different as regeneration temperature, the time of making charcoal, the medium of making charcoal (as the introducing amount of oxygen-containing gas and the oxygen content in the oxygen-containing gas etc.), the selection and the coupling of corresponding operating parameter are well known to those skilled in the art.
One preferred embodiment in, the coke-burning regeneration condition of described step (1) makes in the catalyst after the described regeneration and contains charcoal, the content of described charcoal is no more than 3% of described regenerated catalyst vector contg, is preferably 0.2～2.5%, and more preferably 0.3～2%.
According to method provided by the invention, under the prerequisite on the catalyst that is enough to described phosphorus loaded to after step (1) is made charcoal, will be not particularly limited through method and the condition that the catalyst after make charcoal step (1) contacts with the solution that contains phosphorus-containing compound step (2) is described.For example, can be method by spray, also can be the method for catalyst soakage in described solution after directly just making charcoal.The preferred method that adopts dipping.Wherein, the consumption of the content of phosphorus-containing compound and solution should make in the catalyst after the final regeneration in the described solution, in oxide and with total amount that can not the burn off component in the catalyst is benchmark, Δ P value is 0.1～5 weight %, be preferably 0.2～4 weight %, more preferably 0.3～3 weight %; The increment of phosphorus in the Δ P value representative regeneration rear catalyst, Δ P=P
1%-P
0%, wherein, P
1The phosphorus content of % representative regeneration rear catalyst, P
0Phosphorus content before the % representative regeneration in the agent.The condition of described contact preferably includes: be 0.1～12 hour time of contact, more preferably 0.3～6 hour, be more preferably 0.5～4 hour, and the contact temperature is preferably environment temperature～90 ℃, more preferably environment temperature～70 ℃.
According to method provided by the invention, total amount that can not the burn off component in the described catalyst is meant under air atmosphere in the amount of 4 hours rear catalysts of 550 ℃ of roastings.
The drying of described step (3) is a purpose to remove described solvent, and its method can be any one method that can realize above-mentioned purpose in the prior art.For example, heat drying, drying under reduced pressure and add methods such as thermal drying under reduced pressure.When described drying means was heat drying, preferred baking temperature was no more than 250 ℃, further preferably is no more than 230 ℃, is more preferably and is no more than 200 ℃.For example, one preferred embodiment in, described baking temperature is 100 ℃～200 ℃.
The solution of described phosphorus-containing compound can be the stable solution that described phosphorus-containing compound forms with any solvent that can dissolve described phosphorus-containing compound under normal temperature, condition of normal pressure.Preferred solvent is one or more in water, alcohol or the ammoniacal liquor, more preferably water or ammoniacal liquor.Described phosphorus-containing compound can be selected from one or more in phosphorus pentoxide, phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), trimethyl phosphate, triethyl phosphate, the triphenylphosphine, is preferably phosphoric acid and ammonium salt thereof.
According to method provided by the invention, in described step (2), before or after preferably include the step that at least one introduces organic additive.Under being enough to, the method for introducing organic additive is not particularly limited the prerequisite on the catalyst of described organic additive introducing after step (1) is made charcoal.For example, with described phosphorus-containing compound and described organic additive obtain solution individually or simultaneously, the method for flooding the catalyst that obtains through step (1) afterwards through making charcoal.Wherein, the content of the described organic additive in the described solution, the consumption of solution or dipping number of times, should be enough to make the mol ratio of hydrogenation active metals in the organic matter that is incorporated in the regenerated catalyst and the regenerated catalyst is in 2, is preferably 0.01～2, more preferably 0.03～1.5.When described solution is the mixed solution of described phosphorus-containing compound and described organic additive, the content of phosphorus-containing compound and described organic additive in the described solution, the consumption of solution or dipping number of times should be enough to make in the catalyst after the regeneration, the mol ratio of hydrogenation active metals is in 2 in described organic additive and the regenerated catalyst, be preferably 0.01～2, more preferably 0.03～1.5, here, described hydrogenation active metals is the total amount of hydrogenation active metals, for example when the hydrogenation active metals component was selected from the combination of group VIII and group vib metal, the molal quantity of described hydrogenation active metals was the molal quantity sum that is selected from group VIII and group vib metal; And in oxide and with total amount that can not the burn off component in the catalyst is benchmark, and Δ P value is 0.1～5 weight %, is preferably 0.2～4 weight %, more preferably 0.3～3 weight %.
One preferred embodiment in, described phosphorus and organic additive are the realizations by the described catalyst that obtains through step (1) of the solution impregnation that contains phosphorus-containing compound and organic additive simultaneously, the described solution that contains phosphorus-containing compound and organic additive simultaneously is with P
2O
5The meter, the content of phosphorus-containing compound is 1.4～240 grams per liters, is preferably 3.3 grams per liters～145 grams per liters, the content of organic additive be 0.01～350 mM/liter, be preferably 0.03～220 mM/liter, all the other are solvent.Described solvent is selected from one or more in water, alcohol or the ammoniacal liquor, more preferably water or ammoniacal liquor and mixed liquor thereof.Wherein, the condition of described dipping comprises: dip time is 0.1～12 hour, is preferably 0.3～6 hour, and more preferably 0.5～4 hour, dipping temperature was environment temperature～90 ℃, more preferably environment temperature～70 ℃.
Described organic additive is selected from and contains in oxygen and/or the nitrogenous organic matter one or more.Described oxygenatedchemicals is selected from one or more in organic alcohol, the organic acid, and organic compounds containing nitrogen is selected from one or more in organic amine, the organic ammonium salt.Particularly, be selected from oxygen containing organic matter and be selected from ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200～1500), diethylene glycol, butanediol, acetate, maleic acid, oxalic acid, aminotriacetic acid, 1, in 2-CDTA, citric acid, tartaric acid, the malic acid one or more, wherein preferred ethylene glycol, glycerine, polyethylene glycol and citric acid; Nitrogenous organic matter is selected from one or more in ethylenediamine, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, NTA, EDTA and the ammonium salt thereof, wherein preferred EDTA and NTA.Described organic additive also can comprise simultaneously and contains organic pure and mild organic acid.
When described method comprised the step of introducing organic additive, the drying of described step (3) was a purpose to remove described solvent, and its method can be any one method that can realize above-mentioned purpose in the prior art.For example, heat drying, drying under reduced pressure and add methods such as thermal drying under reduced pressure.When described drying means was heat drying, preferred baking temperature was no more than 250 ℃, further preferably is no more than 230 ℃, is more preferably and is no more than 200 ℃.For example, one preferred embodiment in, described baking temperature is 100 ℃～200 ℃.
According to regeneration hydrogenation catalyst provided by the invention, be benchmark in oxide and with total amount that can not the burn off component in the catalyst, preferred Δ P value is 0.2～4 weight %, more preferably 0.3～3.0 weight %.The increment of phosphorus in the Δ P value representative regeneration rear catalyst, Δ P=P
1%-P
0%, wherein, P
1The phosphorus content of % representative regeneration rear catalyst, P
0Phosphorus content before the % representative regeneration in the agent.
Total amount that can not the burn off component in the described catalyst is meant under air atmosphere in the amount of 4 hours rear catalysts of 550 ℃ of roastings.
Hydrogenation catalyst of the present invention can be the catalyst that any class has hydrogenating function.It particularly is the hydrogenation catalyst of hydrogenation active metals component with the base metal.Comprise Hydrobon catalyst, hydrotreating catalyst or hydrocracking catalyst etc.For example, CN1057021C, the disclosed Hydrobon catalyst of CN1036791C; CN100388977C, the disclosed hydrotreating catalyst of CN1853781A; CN1020282C, the disclosed hydrocracking catalyst of CN1044715C etc.Specifically form about this class catalyst, in above-mentioned invention disclosed patent (application), detailed description is arranged all, incorporate the present invention here in the lump into and quote.
According to regeneration hydrogenation catalyst provided by the invention, wherein also contain carbon, the content of described charcoal is no more than 3% of vector contg in the described catalyst, is preferably 0.2～2.5%, and more preferably 0.3～2%.
According to regeneration hydrogenation catalyst provided by the invention, preferably also contain organic additive, described organic additive is selected from one or more in oxygen-bearing organic matter and/or the itrogenous organic substance, described oxygenatedchemicals is selected from one or more in organic alcohol, the organic acid, and organic compounds containing nitrogen is selected from one or more in organic amine, the organic amine salt.Particularly, described oxygenatedchemicals is selected from oxygen containing organic matter and is selected from ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetate, maleic acid, oxalic acid, aminotriacetic acid, 1, in 2-CDTA, citric acid, tartaric acid, the malic acid one or more, nitrogenous organic matter is selected from one or more in ethylenediamine, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, NTA, EDTA and the ammonium salt thereof.Wherein, the mol ratio of hydrogenation active metals is in 2 in described organic matter and the regenerated catalyst, is preferably 0.01-2, more preferably 0.03-1.5.Here, described hydrogenation active metals is the total amount of hydrogenation active metals, for example when the hydrogenation active metals component was selected from the combination of group VIII and group vib metal, the molal quantity of described hydrogenation active metals was the molal quantity sum that is selected from group VIII and group vib metal.
According to the conventional method in this area, regeneration hydrogenation catalyst provided by the invention is before using, preferably in the presence of hydrogen, under 140-400 ℃ temperature, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out also can original position vulcanizing in device outside device, is translated into sulfide type.
According to hydrogenation method for hydrocarbon oils provided by the invention, can be the reaction that any hydrocarbon ils carries out under hydrogenation conditions.For example, can be hydrofining reaction, hydrotreatment reaction, hydrocracking reaction and hygrogenating isomerization reaction etc.The process conditions that are fit to about all kinds of differential responses of hydrocarbon ils all have detailed description in the book of [hydroprocessing technique and engineering] (Li Dadong chief editor, Sinopec publishing house, 2004), quote as a reference here.For example, the condition of a kind of hydrotreatment of hydrocarbon ils reaction comprises: in the presence of hydrogen, in 200 ℃～420 ℃ of reaction temperatures, hydrogen dividing potential drop 2～18 MPas, liquid hourly space velocity (LHSV) 0.3～10 hour
-1, hydrogen to oil volume ratio 50～5000.
Wherein said hydrocarbon ils comprises: one or more in crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, frivolous coal tar, the heavy deasphalted oil, in the hydrotreatment oil.Particularly comprise: raw materials such as naphtha, kerosene, diesel oil and VGO.
The following examples will the invention will be further described, but not thereby limiting the invention.
Carbon content analytical method: adopt carbon content in the infrared absorption determining catalyst.
Catalyst is formed the employing x ray fluorescence spectrometry and is measured.
Activity level with the desulphurizing activated sign regeneration of the relative volume of regenerated catalyst rear catalyst.
The relative volume of regenerated catalyst is desulphurizing activated=A
HDS-K/ A
HDS-R* 100
A
HDS-KRepresent the desulphurizing activated of the inventive method regenerated catalyst, with A
HDS-RThe activity of expression conventional method regenerated catalyst, and get A
HDS-R=100.
The volume of catalyst is desulphurizing activated can be calculated by following formula.
A wherein
HDSFor desulphurizing activated, LHSV is a volume space velocity, and n is the order of reaction.
Described conventional regeneration method is meant and will treats that regenerative agent carries out the method that roasting obtains regenerative agent in flow air atmosphere, and wherein the sintering temperature scope is 300～500 ℃, and roasting time is 2～12 hours.
Treat regenerated catalyst:
(1) a kind of Hydrobon catalyst a that waits to regenerate, wherein, the content of charcoal be in the described catalyst vector contg 9.3%.In oxide and with total amount that can not the burn off component in the catalyst is benchmark, and the Hydrobon catalyst a that waits to regenerate forms: WO
323.6% weight, MoO
34.2% weight, NiO 2.6% weight, P
2O
50.6% weight, aluminium oxide 69.0% weight.
(2) a kind of hydrotreating catalyst b that waits to regenerate, wherein, the content of charcoal be in the described catalyst vector contg 11.1%.In oxide and with total amount that can not the burn off component in the catalyst is benchmark, and the hydrotreating catalyst b that waits to regenerate forms: WO
329.1% weight, NiO 2.9% weight, F4.3% weight, aluminium oxide 63.7% weight.
(3) a kind of hydrocracking catalyst c of inactivation, wherein, the content of charcoal be in the described catalyst vector contg 8.7%.In oxide and with total amount that can not the burn off component in the catalyst is benchmark, and the hydrocracking catalyst c that waits to regenerate forms: WO
321.0% weight, NiO 4.5% weight, Y zeolite 37.1% weight, aluminium oxide 37.4% weight.
Embodiment 1～7 explanation the invention provides method and regenerated catalyst.
Embodiment 1
1000 grams are treated that regenerated catalyst a places tube furnace, heat temperature raising to 480 ℃ in flow air, air mass flow and reclaimable catalyst ratio are 4 liters/gram, 3 ℃/minute of programming rates, treat that regenerated catalyst a bakes charcoals 3 hours, the A1 catalyst after obtaining making charcoal in 480 ℃.The carbon content of A1 catalyst is 0.45% weight of vehicle weight.
Phosphatase 11 4.6 gram (analyze pure, 85% concentration, Beijing Chemical Plant's product) water is dissolved into 92 ml water solution.With this solution impregnation A1 catalyst 200 grams, dip time is 12 hours.Afterwards, under air atmosphere in 120 ℃ of dryings 4 hours, 220 ℃ dry 3 hours down, obtain regenerated catalyst B.The Δ P value of regenerated catalyst B is listed in table 1.
Embodiment 2
Phosphatase 11 .64 gram (analyzes pure, 85% concentration, Beijing Chemical Plant's product), glycerine 36.6 are restrained (analyze pure, Beijing Chemical Plant's product) water and be dissolved into 92 ml water solution.With this solution impregnation A1 catalyst 200 grams, dip time is 12 hours.Afterwards, under air atmosphere,, obtain regenerated catalyst C in 100 ℃ of dryings 3 hours.Among the regenerated catalyst C organic additive with regenerated catalyst in mol ratio, Δ P value and the carbon content of (Ni+Mo+W) metal list in table 1 respectively.
Embodiment 3
Phosphoric acid 6.4 gram (analyzes pure, 85% concentration, Beijing Chemical Plant's product), EDTA 3.88 are restrained (analyze pure, Beijing Chemical Plant's product) water and be dissolved into 92 ml water solution.With this solution impregnation A1 catalyst 200 grams, dip time is 5 hours.Afterwards, under air atmosphere in 110 ℃ of dryings 4 hours, 160 ℃ dry 3 hours down, obtain regenerated catalyst D.Among the regenerated catalyst D in EDTA and the regenerated catalyst mol ratio of (Ni+Mo+W) metal, Δ P value and carbon content list in table 1 respectively.
Comparative Examples 1
92 ml water solution impregnation A1 catalyst, 200 grams with containing 10 milliliters of EDTA 10.0 grams (analyzes pure, Beijing Chemical Plant's product), ammoniacal liquor (Beijing Chemical Plant's product, 25% concentration are analyzed pure) wore out 12 hours under the room temperature in airtight container behind the dipping.Afterwards, 110 ℃ of dryings are 4 hours under air atmosphere, 160 ℃ dry 3 hours down, obtain regenerated catalyst A2.In the A2 catalyst in EDTA and the regenerated catalyst mol ratio of (Ni+Mo+W) metal be 0.6.
Embodiment 4
1000 grams are treated that regenerated catalyst b places tube furnace, in flow air, heat that programming rate is 3～5 ℃/minute.In the temperature-rise period respectively 230 ℃, 350 ℃ constant temperature 1.5 hours, 400 ℃ of constant temperature 3 hours.Air amount of being blown into and reclaimable catalyst ratio are 4 liters/gram, material are cooled to room temperature, the B1 catalyst after obtaining making charcoal after 400 ℃ of constant temperature finish.The carbon content of B1 catalyst is 1.33% weight of vehicle weight.
Phosphoric acid 3.2 gram (analyzes pure, 85% concentration, Beijing Chemical Plant's product), citric acid 41.2 grams (analyzes pure, the first chemical industry Co., Ltd product that stands in Tianjin) water is dissolved into 80 ml water solution.With this solution impregnation B1 catalyst 200 grams, dip time is 12 hours.Afterwards, under air atmosphere in 120 ℃ of dryings 4 hours, 200 ℃ dry 3 hours down, obtain regenerated catalyst E.Among the regenerated catalyst E in citric acid and the regenerated catalyst mol ratio of (Ni+Mo+W) metal, Δ P value and carbon content list in table 1 respectively.
Embodiment 5
With phosphoric acid 8.8 gram (analyzes pure, 85% concentration, Beijing Chemical Plant's product), EDTA (analyze pure, Beijing Chemical Plant's product) 19.2 restrain, 18 milliliters of waters of ammoniacal liquor (Beijing Chemical Plant's product, 25% concentration are analyzed pure) are dissolved into 80 ml water solution.With this solution impregnation B1 catalyst 200 grams, dip time is 5 hours.Afterwards, under air atmosphere in 110 ℃ of dryings 4 hours, 160 ℃ dry 3 hours down, obtain regenerated catalyst F.Among the regenerated catalyst F in EDTA and the regenerated catalyst mol ratio of (Ni+Mo+W) metal list in table 1 respectively for, Δ P value and carbon content.
Embodiment 6
1000 grams are treated that regenerated catalyst c places tube furnace, in flow air, heat that programming rate is 3 ℃/minute.In the temperature-rise period respectively 230 ℃, 350 ℃ constant temperature 1.5 hours, 450 ℃ of constant temperature 3 hours.Air amount of being blown into and reclaimable catalyst ratio are 4 liters/gram, material are cooled to room temperature, the C1 catalyst after obtaining making charcoal after 450 ℃ of constant temperature finish.The carbon content of C1 catalyst is 1.72% weight of vehicle weight.
Phosphatase 11 .62 gram (analyzes pure, 85% concentration, Beijing Chemical Plant's product), glycerine 29.4 are restrained (analyze pure, Beijing Chemical Plant's product) water and be dissolved into 88 ml water solution.With this solution impregnation C1 catalyst 200 grams, dip time is 6 hours.Afterwards, 100 ℃ were descended dry 3 hours under air atmosphere, obtained regenerated catalyst G.Among the regenerated catalyst G organic additive with regenerated catalyst in mol ratio, Δ P value and the carbon content of (Ni+Mo+W) metal list in table 1 respectively.
Table 1
Comparative Examples 2
The diesel hydrogenation for removal sulphur performance of the regeneration Hydrobon catalyst that this Comparative Examples explanation conventional regeneration technology provides.Be reflected on 30 milliliters of diesel hydrotreating units and carry out, regenerated catalyst is A1, and feedstock oil and reaction condition see Table 2.The results are shown in Table 3.
The assay method of sulphur is SH/T 0253-92.The hydrodesulfurization activity of catalyst calculates by 1.65 order reactions.And definition A1 activity of such catalysts is 100%.Related computing formula is as follows.
Comparative Examples 3
The diesel hydrogenation for removal sulphur performance of the regeneration Hydrobon catalyst that the simple introducing of this Comparative Examples explanation organic additive obtains.Reaction unit, reaction condition and feedstock oil are identical with Comparative Examples 1, and catalyst is A2.The results are shown in Table 3.
Embodiment 8～10
The diesel hydrogenation for removal sulphur performance of regeneration Hydrobon catalyst provided by the invention is described.Reaction unit, reaction condition and feedstock oil are identical with Comparative Examples 1, and catalyst is respectively B, C and D.The results are shown in Table 3.
Table 2
| Feedstock oil character | Straight-run diesel oil |
| Density (20 ℃), g/ml | 0.8456 |
| S，ppm | 8000 |
| N，ppm | 144 |
| Refractive power (20 ℃) | 1.4723 |
| Reaction condition | |
| The hydrogen dividing potential drop, MPa | 3.2 |
| Catalyst volume, ml | 30 |
| Temperature, ℃ | 330 |
| Volume space velocity, h -1 | 2.0 |
| Hydrogen-oil ratio, v/v | 300 |
Table 3
| Catalyst | Desulphurizing activated relatively, % | |
| Comparative Examples 2 | A1 | 100 |
| Embodiment 8 | B | 135 |
| Embodiment 9 | C | 186 |
| Embodiment 10 | D | 165 |
| Comparative Examples 3 | A2 | 147 |
Table 3 is the result show, by in the inactivation Hydrobon catalyst of charcoal regeneration, introducing phosphorus-containing compound, and carry out drying and handle, the resulting catalyst desulfurizing specific activity only catalyst of conventional charcoal regeneration obviously improves, and in the charcoal regeneration catalyst, introduce phosphorus-containing compound and organic matter simultaneously, and carry out drying and handle, can further improve the activity of regenerated catalyst on this basis.
Comparative Examples 4
Decompressed wax oil hydrodesulfurization, the hydrodenitrogeneration performance of the regeneration hydrotreating catalyst that this Comparative Examples explanation conventional regeneration technology provides.Be reflected on 100 milliliters of Wax Oil Hydrogenation Unit and carry out, regenerated catalyst is B1, and feedstock oil and reaction condition see Table 4.The results are shown in Table 5.
The assay method of sulphur is SH/T 0253-92, and the assay method of nitrogen is SH/T 0657-1998.The hydrodesulfurization activity of catalyst calculates by 1.5 order reactions, and hydrodenitrogenationactivity activity is calculated by 1 order reaction.And definition B1 activity of such catalysts is 100%.Related computing formula is as follows.
Table 4
| Feedstock oil character | |
| Density (20 ℃), g/ml | 0.9113 |
| S，ppm | 20000 |
| N，ppm | 1100 |
| Refractive power (70 ℃) | 1.4875 |
| Aniline point, ℃ | 86.3 |
| Reaction condition | |
| The hydrogen dividing potential drop, MPa | 10.0 |
| Catalyst volume, ml | 100 |
| Temperature, ℃ | 375 |
| Volume space velocity, h -1 | 1.0 |
| Hydrogen-oil ratio, v/v | 900 |
Example 11～12
The wax oil hydrogenation desulfurization performance of regeneration hydrotreating catalyst provided by the invention is described.Reaction unit, reaction condition and feedstock oil are identical with Comparative Examples 2, and catalyst is respectively E and F.The results are shown in Table 5.
Table 5
Table 5 is the result show, adopts the inactivation hydrotreating catalyst of the inventive method regeneration, and its relative hydrodesulfurization activity and hydrodenitrogenationactivity activity are significantly higher than the catalyst that adopts conventional charcoal regeneration to obtain.
Comparative Examples 5
The hydrocracking performance of the regeneration hydrocracking catalyst that this Comparative Examples explanation conventional regeneration technology provides.Be reflected on 100 milliliters of hydrogenation plants and carry out, employing is once by flow process, and raw material diesel oil enters cracking zone after refining section is refining, and cracking zone loads regeneration hydrocracking catalyst C1.Feedstock oil character and cracking reaction condition see Table 6, the results are shown in Table 7.
The assay method of Cetane number is GB/T 386-91.＞220 ℃ of diesel oil distillate conversion ratios are calculated as follows and obtain:
＞220 ℃ of diesel oil distillate conversion ratio %=(in the raw material＞220 ℃ of cut content-products in＞220 ℃ of cut content)/raw material in＞220 ℃ of cut content
Table 6
| Refined oil character | Diesel oil |
| Density (20 ℃), g/ml | 0.8845 |
| S，ppm | 2000 |
| N，ppm | 360 |
| Refractive power (20 ℃) | 1.4890 |
| Cetane number | 39.0 |
| Boiling range ASTM D-86, ℃ | |
| Initial boiling point | 215 |
| 50％ | 309 |
| The end point of distillation | 374 |
| Reaction condition | |
| The hydrogen dividing potential drop, MPa | 10.8 |
| Cracking agent volume, ml | 100 |
| Refining section temperature, ℃ | 365 |
| The cracking zone temperature, ℃ | 367 |
| The cumulative volume air speed, h -1 | 1.25 |
| Hydrogen-oil ratio, v/v | 900 |
Example 13
The wax oil hydrogenation desulfurization performance of regeneration hydrotreating catalyst provided by the invention is described.Reaction unit, feedstock oil are all identical with Comparative Examples 3 with reaction condition except that the cracking reaction temperature, and regenerated catalyst is G.The results are shown in Table 7.
Table 7
| Comparative Examples 5 | Example 13 | |
| Catalyst | C1 | G |
| The cracking zone temperature, ℃ | 367 | 358 |
| ＞220 ℃ of diesel oil distillate conversion ratio % | 62.3 | 62.6 |
| The full cut character of product | ||
| Density (20 ℃), g/ml | 0.8102 | 0.8034 |
| Sulphur, ppm | 3.9 | 0.5 |
| Nitrogen, ppm | 0.5 | 0.2 |
| ＞220 ℃ of diesel oil distillate Cetane number | 50.7 | 52.3 |
Table 7 is the result show, compare with conventional charcoal regeneration method, adopt the deactivated commercial hydrocracking catalysts of the inventive method regeneration, under the suitable situation of＞220 ℃ of diesel oil distillate conversion ratios, the cracking reaction temperature is obviously lower, be that activity is higher, and the Cetane number of diesel product (＞220 ℃ of cuts) is also higher.
Claims (15)
1. the renovation process of a hydrogenation catalyst comprises:
(1) under the reaction condition that hydrogenation catalyst regeneration is made charcoal, will treat that regenerated catalyst contacts with oxygen-containing gas;
(2) will contact with the solution that contains phosphorus-containing compound through the catalyst after make charcoal step (1);
(3) will be through the catalyst drying of step (2) contact, the catalyst that obtains regenerating;
Wherein, be benchmark in oxide and with total amount that can not the burn off component in the catalyst, it is 0.1～5 weight % that the contact of described step (2) makes regenerated catalyst Δ P value; The increment of phosphorus in the Δ P value representative regeneration rear catalyst, Δ P=P
1%-P
0%, wherein, P
1The content of phosphorus in the % representative regeneration rear catalyst, P
0The content of phosphorus in the % representative regeneration procatalyst.
2. method according to claim 1 is characterized in that, described Δ P value is 0.2～4 weight %.
3. method according to claim 2 is characterized in that, described Δ P value is 0.3～3 weight %.
4. method according to claim 1, it is characterized in that, described phosphorus-containing compound is selected from one or more in phosphorus pentoxide, phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), trimethyl phosphate, triethyl phosphate, the triphenylphosphine, and the solvent in the described solution is selected from one or more in water, alcohol or the ammoniacal liquor.
5. method according to claim 4 is characterized in that, described phosphorus-containing compound is phosphoric acid and ammonium phosphate salt, and solvent is water or ammoniacal liquor and mixed liquor thereof.
6. method according to claim 1, it is characterized in that, in described step (2) before, simultaneously or comprise that afterwards at least one introduces the step of organic additive, to make the organic additive in the regenerated catalyst and the molar ratio of hydrogenation active metals component be in 2 to the introducing amount of described organic additive.
7. method according to claim 6 is characterized in that, it is 0.03-1.5 that the introducing amount of described organic additive makes the organic additive in the regenerated catalyst and the molar ratio of hydrogenation active metals component.
8. according to claim 6 or 7 described methods, it is characterized in that described organic additive is selected from one or more in organic alcohol, organic acid, organic amine or the organic ammonium salt.
9. method according to claim 8, it is characterized in that, described organic alcohol be selected from ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200～1500), diethylene glycol, the butanediol one or more, organic acid is selected from acetate, maleic acid, oxalic acid, aminotriacetic acid, 1, one or more in 2-CDTA, citric acid, tartaric acid, the malic acid, organic amine are selected from one or more among ethylenediamine, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, NTA, the EDTA.
10. regeneration hydrogenation catalyst is a benchmark in oxide and with total amount that can not the burn off component in the catalyst, and the Δ P value of described regeneration hydrogenation catalyst is 0.1～5 weight %; The increment of phosphorus in the Δ P value representative regeneration rear catalyst, Δ P=P
1%-P
0%, wherein, P
1The content of phosphorus in the % representative regeneration rear catalyst, P
0The content of phosphorus in the % representative regeneration procatalyst.
11., it is characterized in that described Δ P value is 0.2～4 weight % according to the described catalyst of claim 10.
12., it is characterized in that described Δ P value is 0.3～3 weight % according to the described catalyst of claim 11.
13., it is characterized in that according to the described catalyst of claim 10, contain organic additive in the catalyst of described regeneration, the mol ratio of described organic additive and hydrogenation active metals component is in 2.
14. method according to claim 13 is characterized in that, the mol ratio of described organic additive and hydrogenation active metals component is 0.03～1.5.
15. a hydrogenation method for hydrocarbon oils is included under the hydrogenation conditions hydrocarbon ils is contacted with catalyst, it is characterized in that described catalyst is any described regeneration hydrogenation catalyst of claim 10～14.
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| US4485183A (en) * | 1982-04-12 | 1984-11-27 | Union Oil Company Of California | Regeneration and reactivation of deactivated hydrorefining catalyst |
| CN1107700C (en) * | 2000-07-24 | 2003-05-07 | 中国石油化工股份有限公司 | Method of regenerating hydrogenation cracking catalyst |
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| CN1488442A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Catalyst reactivating method |
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