CN1552521A - Method for preparing hydrofining catalyst by waste catalyst - Google Patents
Method for preparing hydrofining catalyst by waste catalyst Download PDFInfo
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- CN1552521A CN1552521A CNA031335586A CN03133558A CN1552521A CN 1552521 A CN1552521 A CN 1552521A CN A031335586 A CNA031335586 A CN A031335586A CN 03133558 A CN03133558 A CN 03133558A CN 1552521 A CN1552521 A CN 1552521A
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Abstract
A process for preparing the hydrorefining catalyst from the used one includes such steps as adding less active metal component to the used hydrorefining catalyst powder and activating (regenerating). It features that in said regeneration procedure, the metallic salt is decomposed to absorb heat and generate gas to improve the artery structure of catalyst.
Description
Technical field
The present invention relates to a kind ofly prepare the method for Hydrobon catalyst, particularly can not satisfy the method that useless Hydrobon catalyst that reaction process requires prepares Hydrobon catalyst by reactivity worth by spent catalyst.
Background technology
The annual whole world will produce a large amount of can't carry out the useless Hydrobon catalyst of regenerated.The filler of industries such as building is generally selected these spent catalyst are abandoned or are used as by the refinery, but the problem that has two aspects: 1. because generally contain molybdenum that total amount is about 20w%～40w%, tungsten, cobalt, nickel etc. in the Hydrobon catalyst worth metal oxide is arranged, so processing can cause the wasting of resources.2. the catalyzer that abandons is owing to the loss of above-mentioned metal will pollute environment, especially to water resources.Given this, a lot of countries forbid now how these spent catalyst are disposed is the problem that the researchist extremely is concerned about always to arbitrarily the abandoning or his usefulness of spent catalyst.
How better dispose in the existing scheme of useless Hydrobon catalyst, the most frequently used is that the catalyzer degradation is used, that is to say, though catalyst activity can not satisfy existing requirement, but its regeneration can be made it to be used for the lower course of processing of other active requirement, can improve the rate of utilization of catalyzer like this, but this method can not solve the handling problems of final spent catalyst.
It is a kind of selection preferably that metal in the spent catalyst is reclaimed, and so not only can economize on resources, and can prevent that the metal pair environment in the spent catalyst from polluting.The recovery of metal generally adopts extraction process in the majority, also has to use substitution method.Chinese patent CN1072730C has introduced a kind of cobalt-molybdenum catalyst recovery method, to the ammonia of the useless cobalt-molybdenum catalyzer dipping solution that repeatedly circulates, with the cobalt in the zinc displacement complex compound, adds nitric acid afterwards and reclaims MoO earlier
3, the filter residue sulfuric acid dissolution after ammonia soaks adds ammonium sulfate and isolates tschermigite, to remove most of aluminium; The a small amount of concentrated solution of gained removes after the impurity such as iron, adds excess ammonia and makes cobalt form complex compound, goes out cobalt with zinc dust precipitation again.Metal recovery processes is a kind ofly to select preferably for the catalyzer that has really had no value for use, but himself benefit and not obvious.Especially in China because the price of Hydrobon catalyst loaded metal is relatively cheap, so from useless Hydrobon catalyst, extract reclaim metal except environmental benefit better, economic benefit is also not obvious.So, also should further inquire into the handling problems of spent catalyst.
Useless Hydrobon catalyst itself also has certain activity, and the main physical and chemical performance index in back of especially regenerating is still similar with live catalyst.These catalyzer suffer the depleted major cause to be: 1. the pore passage structure of catalyzer self is compared with live catalyst with acid matter and be there are differences.2. because accumulation of metal, surface metal take place for it crosses by force etc. to catalyzer internal migration, metal and carrier interphase interaction, cause part metals in long-term operation and regenerative process, especially the metal of catalyst surface loses activity or activity can not get bringing into play.3. the impurity deposition is too much on the catalyzer.Make and to continue to use by the depleted catalyzer, key is to improve the activity of spent catalyst itself, one of selectable method be exactly in spent catalyst, to add a certain amount of material with improve its pore passage structure and acid matter or (with) amount of reactive metal on the make-up catalyst.Patent US4,888,316 have introduced a kind of treatment process of useless Hydrobon catalyst, with useless Hydrobon catalyst through grinding, adding salic material, moulding and treating processes such as make charcoal, especially add salic material and can improve pore canal structure of catalyst and acidity, also can use after making spent catalyst regeneration.But this patent has only solved problem how to improve catalyzer duct structure and acid matter, does not relate to how reactive metal composition on the catalyzer being replenished.In addition, do not find that other amount by replenishing reactive metal on the spent catalyst is so that the report that spent catalyst reuses yet.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of method that can effectively utilize useless Hydrobon catalyst, this method can economize on resources, increase the benefit, and is easy to technically implement.
The inventive method may further comprise the steps:
A, the Hydrobon catalyst that will give up are ground to 100～400 orders, are preferably 200～300 orders;
B, in the powder that steps A obtains, add active metal oxide or the reactive metal salt be used for the Hydrobon catalyst preparation;
C, in the powder that step B obtains, add caking agent, it is mixed pinch, moulding;
D, the forming composition that the C step is obtained are carried out manipulation of regeneration.
Wherein the reactive metal in active metal oxide described in the step B or the reactive metal salt is one or more in molybdenum, tungsten, cobalt and the nickel, select for use one or more bimetals among Mo-Co, Mo-Ni, W-Co and the W-Ni relatively good, preferably select the reactive metal identical for use with the kind of the used metal of raw catalyst, the reactive metal amount that is added accounts for the 1w%～15w% of total metal content on the spent catalyst, is preferably 2w%～10w%.
The bonding dosage that adds among the step C accounts for the 10w%～30w% of spent catalyst weight, is preferably 15w%～25w%.
The described regenerative process of step D is: the regenerating unit of at first catalyzer being packed into, with rare gas element device is replaced earlier, then oxygen level is progressively increased and be 0.5v%～10.0v%, be preferably 1.0v%～5.0v%, catalyzer is carried out the substep coke-burning regeneration.Generally can divide four-stage to regenerate, each stage major control condition is: at 100～140 ℃, be preferably 110～120 ℃, constant temperature 1～3h; At 150～240 ℃, be preferably 170～220 ℃, constant temperature 1～3h; At 250～350 ℃, be preferably 260～320 ℃, constant temperature 1～2h; At 450～550 ℃, be preferably 480～510 ℃, constant temperature 2～4h.
Said process is because the metal component that adds provides new reactive metal position for catalyzer, and after the catalyzer roasting (regeneration), activity will be improved undoubtedly, can be used for former hydrogenation reaction or other reaction process.
If reactive metal adds with the metallic salt form, these metallic salts will absorb heat owing to decomposition in regenerative process, the heat release when helping to control contained spent catalyst regeneration, and preventing that catalyzer is sintered influences catalyst performance.In addition, if reactive metal adds with the metallic salt form, the gas that produces when these salts decompose is to improving pore canal structure of catalyst also with helpful.
The useless Hydrobon catalyst that the present invention relates to comprises that activity has not reached former reaction requirement, or thinks catalyzer such as the hydrogenating desulfurization that can not continue to use, hydrodenitrification, residual hydrogenation.Reactive metal on this Hydrobon catalyst is the metal of VIB, VIIB and/or VIII family, preferably one or more among W, Mo, Co, the Ni.Except the sulfide of reactive metal, comprise that also aluminum oxide and/or other are as impurity such as titanium oxide, boron oxide, silicon oxide, pure aluminium silicate, zeolite etc. and carbon deposit, heavy metals in the useless Hydrobon catalyst.Active metallic content on the spent catalyst generally accounts for 1.0～40.0wt% of catalyst weight, and the content of beavy metal impurity generally accounts for 0.1～10.0wt%.Shape generally is cylindrical, spherical or leafy shape, and diameter is 0.5～3.5mm, and length is 1.5～10.0mm.
In the present invention, the active metal oxide that is added contains MoO
3, WO
3, among CoO, the NiO one or more, be more preferably to add and contain one or more MoO
3-CoO, MoO
3-NiO, WO
3-CoO, WO
3-NiO bimetal preferably adds the bimetal identical with the raw catalyst metal species.
In the present invention, the reactive metal salt that is added contains nickelous nitrate, Xiao Suangu, basic nickel carbonate, cobaltous dihydroxycarbonate, ammonium metawolframate, the metamolybdic acid ammonium, nickel hydroxide, in the cobaltous hydroxide etc. one or more, be more preferably to add and contain one or more metamolybdic acid ammonium-Xiao Suangus, metamolybdic acid ammonium-cobaltous dihydroxycarbonate, metamolybdic acid ammonium-cobaltous hydroxide, metamolybdic acid ammonium-nickelous nitrate, metamolybdic acid ammonium-basic nickel carbonate, metamolybdic acid ammonium-nickel hydroxide, ammonium metawolframate-Xiao Suangu, ammonium metawolframate-cobaltous dihydroxycarbonate, ammonium metawolframate-cobaltous hydroxide, ammonium metawolframate-nickelous nitrate, ammonium metawolframate-basic nickel carbonate, ammonium metawolframate-nickel hydroxide bimetal salts etc. preferably add the bimetal salt identical with the raw catalyst metal species.
In the present invention, active metal oxide or reactive metal salt can be sneaked into, and the form that the reactive metal salt also can the aqueous solution adds.
Method of the present invention compared with prior art has the following advantages and characteristics:
1, the inventive method can improve activity of such catalysts by add a spot of active metal component regenerated method then in useless Hydrobon catalyst powder, makes this spent catalyst be continued to use, thereby reaches aim of saving.
2, reactive metal adds with the metallic salt form, and these metallic salts will absorb heat owing to decomposition in regenerative process, the heat release when helping to control contained spent catalyst regeneration, and preventing that catalyzer is sintered influences catalyst performance.
3, reactive metal adds with the metallic salt form, and the gas that produces when these salts decompose helps to improve pore canal structure of catalyst.
4, method of the present invention is simple, operation easy to implement.
Embodiment
Advance-go on foot to describe in detail method of the present invention below by embodiment and comparative example.
The total acid of catalyzer, B acid and L acid are measured on NiCOLET-560 type infrared spectrophotometer in following examples.The relative reactivity of catalyzer is estimated on anti-little.Main operational condition is catalyst levels: 10ml; Stock oil: 2160ppm thiophene/lam-oil; Volume space velocity: 1.8h
-1Reaction pressure: 4.0MPa; Hydrogen flow rate: 120ml/min.
Embodiment 1
At first, the W-Ni/Al that will give up
2O
3Hydrobon catalyst (contains 27.86w%WO
3, 2.39w%NiO, 6.61w%C, 6.01w%S, 0.06w%Fe, surplus is Al
2O
3) be ground to 250 orders; Then, sneak into the WO of 2.0w%
3Porphyrize adds the binding agent moulding of 20w% again; Then, under the following conditions this catalyzer is regenerated (activation): with the catalyzer regenerating unit of packing into, with inert nitrogen gas device is replaced earlier, then oxygen level is progressively increased to 2.5v% heats up constant temperature 2h, constant temperature 2h 200 ℃ time the, constant temperature 1.5h 290 ℃ time the, constant temperature 3h 490 ℃ time the in the time of 120 ℃.The gained deactivated catalyst be numbered A.
Embodiment 2
The useless W-Ni/Al that uses among the embodiment 1
2O
3The Hydrobon catalyst powder, being 2.0w% with total CoO content, cobalt nitrate solution soaks, and adds the binding agent moulding of 20w% after 120 ℃ of oven dry.Then under the condition identical with embodiment 1 to catalyst activation.Resultant catalyzer be numbered B.
Embodiment 3
The useless W-Ni/Al that uses among the embodiment 1
2O
3The Hydrobon catalyst powder is sneaked into the MoO of 1.0w%
3, 0.8w% WO
3With the CoO porphyrize of 0.2w%, and the binding agent moulding of interpolation 20w%.Then under the condition identical with embodiment 1 to catalyst regeneration.The gained catalyzer be numbered C.
Embodiment 4
The useless W-Ni/Al that uses among the embodiment 1
2O
3The Hydrobon catalyst powder is sneaked into the WO of 1.8w%
3With the NiO porphyrize of 0.2w%, and the binding agent moulding of interpolation 20w%.Then under the condition identical with embodiment 1 to catalyst activation.The gained catalyzer be numbered D.
Embodiment 5
The useless W-Ni/Al that uses among the embodiment 1
2O
3The Hydrobon catalyst powder is 0.2w% and total WO with total NiO content
3Content is ammonium metawolframate-basic nickel carbonate solution soaking of 1.8w%, adds the binding agent moulding of 20w% after 120 ℃ of oven dry.Then under the condition identical with embodiment 1 to catalyst activation.The gained catalyzer be numbered E.
Comparative example 1
The useless W-Ni/Al that uses among the embodiment 1
2O
3The Hydrobon catalyst powder adds the binding agent moulding of 20w%.Then under the condition identical with embodiment 1 to catalyst activation.The gained catalyzer be numbered F.
Embodiment 1～5, and the physical and chemical performance and the activity rating result that obtain catalyzer in the comparative example 1 all see Table 1.
Obtain the physical and chemical performance and the activity rating result of catalyzer in table 1 embodiment 1～5 and the Comparative Examples 1
| The catalyzer numbering | ????A | ????B | ????C | ????D | ????E | ????F |
| Physico-chemical property: specific surface area, mm 2/ g pore volume, cm 3/ g mean pore size, the nm total acid, mmol/g B acid, mmol/g L acid, mmol/g thing phase relative reactivity, % | ????98.3 ????0.14 ????5.70 ????0.145 ????0.106 ????0.039 ????γ-Al 2O 3????105 | ????98.5 ????0.16 ????6.50 ????0.152 ????0.107 ????0.045 ????γ-Al 2O 3????104 | ????92.8 ????0.14 ????6.03 ????0.156 ????0.110 ????0.046 ????γ-Al 2O 3????108 | ????96.6 ????0.14 ????5.80 ????0.150 ????0.106 ????0.044 ????γ-Al 2O 3????108 | ????99.2 ????0.16 ????6.45 ????0.161 ????0.116 ????0.045 ????γ-Al 2O 3????110 | ????98.4 ????0.15 ????6.25 ????0.135 ????0.104 ????0.031 ????γ-Al 2O 3????100 |
As can be seen from Table 1, if be benchmark with the relative reactivity of the catalyzer that obtains in the comparative example 1, in spent catalyst, add reactive metal activation (regeneration) after, reactive metal state of aggregation species do not appear in catalyst surface, acidity, especially activity have significant increase.Find also that in addition with the catalyzer that the salts solution of reactive metal is handled, its pore volume has certain increase.
Embodiment 6
At first, the Mo-Co/Al that will give up
2O
3The Hydrobon catalyst powder (contains 18.46w%MoO
3, 3.54w%CoO, 11.30w%C, 4.71w%S, 0.05w%Fe, surplus is Al
2O
3) be ground to 140 orders; Then, be 0.05w% and total WO with total NiO content
3Content is that ammonium metawolframate-basic nickel carbonate-nickel nitrate solution of 0.2w% soaks, and adds the binding agent moulding of 15w% after 120 ℃ of oven dry; Then, under the following conditions this catalyzer is regenerated (activation): with the catalyzer regenerating unit of packing into, with rare gas element device is replaced earlier, then oxygen level is progressively increased to 1.0v% heats up constant temperature 1h, constant temperature 1h 230 ℃ time the, constant temperature 1h 340 ℃ time the, constant temperature 4h 470 ℃ time the in the time of 110 ℃.The gained deactivated catalyst be numbered G.
Embodiment 7
The useless Mo-Co/Al that uses among the embodiment 6
2O
3The Hydrobon catalyst powder is 0.65w% and total WO with total NiO content
3Content is that ammonium metawolframate-basic nickel carbonate-nickel nitrate solution of 2.0w% soaks, and adds the binding agent moulding of 25w% after 120 ℃ of oven dry.Then under the condition identical with embodiment 1 to catalyst activation.The gained catalyzer be numbered H.
Obtain the physical and chemical performance and the activity rating result of catalyzer in table 2 embodiment 6,7 and the Comparative Examples 1
| The catalyzer numbering | ????G | H | ????F |
| Pore volume, cm 3/ g total acid, mmol/g thing phase relative reactivity, % | ????0.15 ????0.138 ????γ-Al 2O 3????103 | 0.18 0.181 small amount of N iWO 4，γ-Al 2O 3111 | ????0.15 ????0.135 ????γ-Al 2O 3????100 |
As can be seen from Table 2, use with embodiment 1～5 granularity different catalysts powder, the reactive metal that adds different content and binding agent, change activation condition under, its activity of catalyzer of handling with this method still has raising in various degree.
Claims (11)
1, a kind ofly prepare the method for Hydrobon catalyst, may further comprise the steps by spent catalyst:
A, the Hydrobon catalyst that will give up are ground to 100～400 orders;
B, in the powder that steps A obtains, add active metal oxide or the reactive metal salt be used for the Hydrobon catalyst preparation;
C, in the powder that step B obtains, add caking agent, it is mixed pinch, moulding;
D, the forming composition that the C step is obtained are carried out manipulation of regeneration.
2, according to claim 1ly prepare the method for Hydrobon catalyst, it is characterized in that the described Hydrobon catalyst that will give up of steps A is ground to 200～300 orders by spent catalyst.
3, according to claim 1ly prepare the method for Hydrobon catalyst, it is characterized in that reactive metal in active metal oxide described in the step B and the reactive metal salt is one or more in molybdenum, tungsten, cobalt and the nickel by spent catalyst.
4, according to claim 1ly prepare the method for Hydrobon catalyst, it is characterized in that the described reactive metal of step B is one or more bimetals among Mo-Co, Mo-Ni, W-Co and the W-Ni by spent catalyst.
5, describedly prepare the method for Hydrobon catalyst according to claim 1,3 or 4, it is characterized in that the described reactive metal of step B is identical with the kind of the used metal of raw catalyst by spent catalyst.
6, according to claim 1ly prepare the method for Hydrobon catalyst, it is characterized in that reactive metal amount that step B is added accounts for the 1w%～15w% of total metal content on the spent catalyst by spent catalyst.
7, according to claim 1ly prepare the method for Hydrobon catalyst, it is characterized in that reactive metal amount that step B is added accounts for the 2w%～10w% of total metal content on the spent catalyst by spent catalyst.
8, according to claim 1ly prepare the method for Hydrobon catalyst, it is characterized in that the caking agent that adds among the step C accounts for the 10w%～30w% of spent catalyst weight by spent catalyst.
9, according to claim 1ly prepare the method for Hydrobon catalyst, it is characterized in that the caking agent that adds among the step C accounts for the 15w%～25w% of spent catalyst weight by spent catalyst.
10, according to claim 1ly prepare the method for Hydrobon catalyst by spent catalyst, it is characterized in that the described regenerative process of step D is divided into four-stage, the processing condition of control are: at 100～140 ℃, and constant temperature 1～3h; At 150～240 ℃, constant temperature 1～3h; At 250～350 ℃, constant temperature 1～2h; At 450～550 ℃, constant temperature 2～4h.
11, according to claim 1ly prepare the method for Hydrobon catalyst by spent catalyst, it is characterized in that the described regenerative process of step D is divided into four-stage, the processing condition of control are: at 110～120 ℃, and constant temperature 1～3h; At 170～220 ℃, constant temperature 1～3h; At 260～320 ℃, constant temperature 1～2h; At 480～510 ℃, constant temperature 2～4h.
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| CN102441440A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing hydrotreating catalyst from waste catalyst |
| CN102580765A (en) * | 2011-01-06 | 2012-07-18 | 中国科学院过程工程研究所 | Reproduction method of coal tar hydrofining catalyst |
| CN103230798A (en) * | 2013-04-26 | 2013-08-07 | 沈阳三聚凯特催化剂有限公司 | Hydrogen desulfurization catalyst and preparation method thereof |
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| CN102441440A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing hydrotreating catalyst from waste catalyst |
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| CN102580765A (en) * | 2011-01-06 | 2012-07-18 | 中国科学院过程工程研究所 | Reproduction method of coal tar hydrofining catalyst |
| CN103506134A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Low-cost hydrocarbon steam-reforming catalyst and preparation method thereof |
| CN103506122A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Low-cost hydrogen production catalyst and preparation method thereof |
| CN103506122B (en) * | 2012-06-27 | 2015-10-07 | 中国石油化工股份有限公司 | Low-cost hydrogen production catalyst and preparation method thereof |
| CN103506134B (en) * | 2012-06-27 | 2016-03-02 | 中国石油化工股份有限公司 | Low cost hydrocarbon steam conversion catalyst and preparation method thereof |
| CN103769173A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for utilizing waste hydro-treatment catalyst |
| CN104046388A (en) * | 2013-03-14 | 2014-09-17 | 北京宝塔三聚能源科技有限公司 | Hydrogenation thermal decomposition catalyst and method for preparation of fuel oil from the same |
| CN104046388B (en) * | 2013-03-14 | 2015-11-18 | 北京宝塔三聚能源科技有限公司 | A kind of heat from hydrogenation decomposition catalyst and use it to prepare the method for oil fuel |
| CN103230798A (en) * | 2013-04-26 | 2013-08-07 | 沈阳三聚凯特催化剂有限公司 | Hydrogen desulfurization catalyst and preparation method thereof |
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