CN1290617C - Process for preparing hydrogenating refining catalyst by waste hydrogenating refining catalyst - Google Patents
Process for preparing hydrogenating refining catalyst by waste hydrogenating refining catalyst Download PDFInfo
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- CN1290617C CN1290617C CN 03134001 CN03134001A CN1290617C CN 1290617 C CN1290617 C CN 1290617C CN 03134001 CN03134001 CN 03134001 CN 03134001 A CN03134001 A CN 03134001A CN 1290617 C CN1290617 C CN 1290617C
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Abstract
The present invention relates to a method for preparing a hydrorefining catalyst from a spent hydrorefining catalyst. The method of the present invention comprises: active metal components and an alumina containing substance for preparing a hydrogenation catalyst are added into spent hydrorefining catalyst powder, and then the spent hydrorefining catalyst powder is regenerated. The method can improve the activity of the catalyst so that the spent catalyst continues to be used, and consequently, the purpose of resource saving is achieved. Heat is absorbed owing to the decomposition of the metallic salts and the decomposition of the hydrated alumina in the catalyst regeneration process when active metals are added in the forms of metallic salts, the alumina containing substance and hydrated alumina, which is helpful to the control of the heat release of the contained spent catalyst during regeneration, and the catalyst is prevented from being sintered to influence the catalyst performance. Additionally, gas generated when the salts are decomposed is helpful to the pore canal structure improvement of the catalyst in the regeneration process.
Description
Technical field
The present invention relates to a kind of method for preparing Hydrobon catalyst, particularly can not satisfy the method that useless Hydrobon catalyst that course of reaction requires prepares Hydrobon catalyst by reactivity worth.
Background technology
The annual whole world will produce a large amount of useless Hydrobon catalysts that can't regenerate.The filler of industries such as building is generally selected these dead 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 20wt%～40wt%, tungsten, cobalt, nickel etc. in the Hydrobon catalyst worth metal oxide is arranged, so processing can cause the wasting of resources.2. the catalyst that abandons is owing to the loss of above-mentioned metal will pollute environment, especially to water resource.Given this, a lot of countries forbid now how these dead catalyst are disposed is the problem that the researcher extremely is concerned about always to arbitrarily the abandoning or his usefulness of dead catalyst.
How better dispose in the existing scheme of useless Hydrobon catalyst, the most frequently used is that the catalyst 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 process of other active requirement, can improve the utilization rate of catalyst like this, but this method can not solve the handling problems of final dead catalyst.
It is a kind of selection preferably that metal in the dead catalyst is reclaimed, and so not only can economize on resources, and can prevent that the metal pair environment in the dead catalyst from polluting.The recovery of metal generally adopts extraction in the majority, also has to use displacement method.CN 1072730C has introduced a kind of cobalt-molybdenum catalyst recovery method, to the ammonia of the useless cobalt-molybdenum series catalyst 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 ammonia-alum, to remove most of aluminium; The a small amount of concentrate 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 catalyst that has really had no value for use, but himself benefit and not obvious.Especially in China because the price of Hydrobon catalyst carried 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 dead 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 fresh catalyst.The main cause that these catalyst are discarded is: 1. the pore passage structure of catalyst self is compared with fresh 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 catalyst 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 catalyst.Make the catalyst that will discard can also continue to use, key is to improve the activity of dead catalyst itself, and the method that adopts is exactly to add a certain amount of material to improve its pore passage structure and acid matter in dead catalyst at present.Patent USP 4,888,316 have introduced a kind of processing method of useless Hydrobon catalyst, with useless Hydrobon catalyst through grinding, adding salic material, moulding and processing procedure such as make charcoal, especially add salic material and can improve pore canal structure of catalyst and acidity, also can use after making dead catalyst regeneration.But so only solved problem how to improve catalyst duct structure and acid matter, do not related to and how reactive metal composition on the catalyst being replenished.So, how to adopt the better method Hydrobon catalyst that will give up to be converted into the hydrogenation catalyst that can continue to use and still to need further discussion.
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 the Hydrobon catalyst that gives up to prepare 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, useless Hydrobon catalyst are ground to 100～400 orders, are preferably 200～300 orders;
B, the salic material that adding simultaneously is used to prepare the reactive metal oxides or the reactive metal salt of Hydrobon catalyst and is used to prepare hydrogenation catalyst in the powder that steps A obtains;
C, in the powder that step B obtains, add bonding agent, it is mixed pinch, moulding;
The processing of regenerating of D, the article shaped that the C step is obtained.
Wherein the reactive metal in reactive metal oxides 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 bimetallics 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 1wt%～80wt% of reactive metal total amount on the dead catalyst, is preferably 2wt%～30wt%.The described salic material that is used to prepare hydrogenation catalyst is alumina-based supports and/or hydrated alumina.Alumina-based supports is γ-Al
2O
3, titaniferous, silicon, zirconium, phosphorus or boron gama-alumina (wherein the content of gama-alumina is greater than 50wt%) in one or more, wherein hydrated alumina is a water aluminium oxide and/or a boehmite, preferably selects salic material used when preparing with dead catalyst for use.The granularity of the salic material that is added is 100～400 orders.The salic material that is added and the weight ratio of initiate reactive metal are the 60-150% of salic material and reactive metal weight ratio in the dead catalyst, are preferably 80-120%.
The weight of the bonding agent that adds among the step C accounts for 10%～30% of the resultant substance weight of step B, is preferably 15%～25%.
The described regenerative process of step D is: the regenerating unit of at first catalyst being packed into, and use inert gas (as N earlier
2, Ar etc.) device is replaced, then oxygen content is transferred to 0.5v%～10.0v%, be preferably 1.0v%～5.0v%, catalyst 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 catalyst, and behind the catalyst regeneration, hydrogenation activity will be improved undoubtedly.
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 dead catalyst regeneration, and preventing that catalyst 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.
Said process can improve the pore passage structure and the acidity of dead catalyst greatly owing to added new carrier components, and this will help to increase activity of such catalysts node and response location number, and refining activity will improve.
If carrier adds with the hydrated alumina form, these materials will absorb heat owing to heat release in regenerative process, and the concentrated heat release when helping to reduce dead catalyst regeneration prevents that catalyst is sintered.In addition, if carrier adds with the form of hydrate, the gas that produces during these decomposition of hydrate is to improving pore canal structure of catalyst also with helpful.
In the said process,, can improve the hydrogenation activity and the refining activity of catalyst simultaneously owing to added reactive metal and carrier simultaneously.
The useless Hydrobon catalyst that the present invention relates to comprises that activity has not reached former reaction requirement, or thinks catalyst such as the hydrodesulfurization that can not continue to use, hydrodenitrogeneration, 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 aluminium oxide and/or other are as impurity such as titanium oxide, boron oxide, silica, alumina silicate, zeolite etc. and carbon deposit, heavy metals in the useless Hydrobon catalyst.Active metallic content on the dead 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 reactive metal oxides 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 bimetallic oxide preferably adds the reactive metal oxides identical with the raw catalyst metal species.
In the present invention, the reactive metal salt that is added contains nickel nitrate, cobalt nitrate, basic nickel carbonate, basic cobaltous carbonate, ammonium metatungstate, the metamolybdic acid ammonium, nickel hydroxide, in the cobalt hydroxide etc. one or more, be more preferably to add and contain one or more metamolybdic acid ammonium-cobalt nitrates, metamolybdic acid ammonium-basic cobaltous carbonate, metamolybdic acid ammonium-cobalt hydroxide, metamolybdic acid ammonium-nickel nitrate, metamolybdic acid ammonium-basic nickel carbonate, metamolybdic acid ammonium-nickel hydroxide, ammonium metatungstate-cobalt nitrate, ammonium metatungstate-basic cobaltous carbonate, ammonium metatungstate-cobalt hydroxide, ammonium metatungstate-nickel nitrate, ammonium metatungstate-basic nickel carbonate, ammonium metatungstate-nickel hydroxide bimetallic salt preferably adds the metallic salt identical with the raw catalyst metal species.
In the present invention, reactive metal oxides or reactive metal salt can be sneaked into, and the form that the reactive metal salt also can its aqueous solution is introduced; The adding mode of salic material is the method for sneaking into.
Method of the present invention compared with prior art has the following advantages and characteristics:
1, the inventive method is by adding a spot of active metal component and being used for the method that the salic material of unifining process is regenerated then in useless Hydrobon catalyst powder, can increase hydrogenation sites and refining activated centre on the catalyst simultaneously, improve activity of such catalysts, make this dead catalyst be continued to use, thereby reach aim of saving.
2, reactive metal adds fashionable with metallic salt, salic material with the form of hydrated alumina, these metallic salts and hydrated alumina will absorb heat owing to decomposition in regenerative process, heat release when helping to control contained dead catalyst regeneration, preventing that catalyst is sintered influences catalyst performance.
3, reactive metal adds fashionablely with the form of hydrated alumina with metallic salt, salic material, and the gas that produces when these salts and decomposition of hydrate helps to improve pore canal structure of catalyst.
4, method of the present invention is simple, operation easy to implement.
The specific embodiment
Be described in further detail method of the present invention below by embodiment and comparative example.
The specific area of catalyst, pore volume and average pore size are to carry out on the ASAP2400 physical adsorption appearance that U.S. Mai Ke company produces in following examples; Total acid, B acid and L acid are measured on NiCOLET-560 type infrared spectrophotometer.The HDS relative activity is estimated on anti-little, and main operating condition is catalyst amount: 10ml; Feedstock oil: 2160ppm thiophene/lam-oil; Volume space velocity: 1.8h
-1Temperature: 320 ℃; Reaction pressure: 4.0MPa; Hydrogen flow rate: 120ml/min.The main operating condition of HDN relative activity evaluation is catalyst amount: 10ml; Feedstock oil: 950ppm pyridine/lam-oil; Volume space velocity: 2.0h
-1Temperature: 360 ℃: reaction pressure: 4.0MPa; Hydrogen flow rate: 100ml/min.
Embodiment 1
Get a kind of granularity and be the useless W-Ni/Al about 250 orders
2O
3The Hydrobon catalyst powder (contains 27.86wt%WO
3, 2.39wt%NiO, 6.61wt%C, 6.01wt%S, 0.06wt%Fe, surplus is Al
2O
3) 20.0g, adding granularity is 250 order 0.9g WO
3(specific area is 241m with 1.6g titanium dioxide-aluminium oxide
2/ g, pore volume are 0.60cm
3/ g, average pore size is 9.0nm, contains titanium dioxide 5.32wt%) and mixing, add the moulding of 4.5g bonding agent.Under the following conditions this catalyst is regenerated then: with the catalyst regenerating unit of packing into, with nitrogen device is replaced earlier, then oxygen content is transferred to and begin behind the 2.50v% to heat 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 regenerated catalyst be numbered A.
Embodiment 2
Get the useless W-Ni/Al that uses among the embodiment 1
2O
3Hydrobon catalyst powder 20.0g, with the cobalt nitrate solution immersion of 40ml, 2.25wt%, (can obtain specific area after the roasting is 282m to add 1.8g one water aluminium oxide after 120 ℃ of oven dry
2/ g, pore volume are 0.63cm
3/ g, average pore size is the gama-alumina of 9.0nm) and porphyrize to 250 order, add the moulding of 4.5g bonding agent.Then under the condition identical with embodiment 1 to catalyst regeneration.Resultant catalyst be numbered B.
Embodiment 3
Get the useless W-Ni/Al that uses among the embodiment 1
2O
3Hydrobon catalyst powder 20.0g sneaks into 0.4gMoO
3, 0.4gWO
3With 0.1gCoO and granularity be that (specific area is 272m to 250 purpose 0.8g silica/alumina
2/ g, pore volume are 0.62cm
3/ g, average pore size is 9.1nm, contains silica 1 .25wt%) and 0.8g diboron trioxide-aluminium oxide (specific area is 234m
2/ g, pore volume are 0.63cm
3/ g, average pore size is 10.8nm, trioxygen-containingization two boron 5.05wt%) and mixing, add the moulding of 4.5g bonding agent.Then under the condition identical with embodiment 1 to catalyst regeneration.The gained catalyst be numbered C.
Embodiment 4
Get the useless W-Ni/Al that uses among the embodiment 1
2O
3Hydrobon catalyst powder 20.0g sneaks into 0.8gWO
3With 0.1gNiO and granularity be that (specific area is 251m to 250 purpose 0.24g zirconium dioxide/aluminium oxide
2/ g, pore volume are 0.58cm
3/ g, average pore size is 9.3nm, contains zirconium dioxide 6.34wt%), (specific area is 230m to 0.96g phosphorus pentoxide-aluminium oxide
2/ g, pore volume are 0.53cm
3/ g, average pore size is 9.3nm, contains phosphorus pentoxide 3.45wt%) and the 0.50gwt% boehmite (can obtain specific area after the roasting is 329m
2/ g, pore volume are 0.62cm
3/ g, average pore size is the gama-alumina of 9.1nm), and mixing, add the moulding of 4.5g bonding agent.Then under the condition identical with embodiment 1 to catalyst regeneration.The gained catalyst be numbered D.
Embodiment 5
The useless W-Ni/Al that uses among the embodiment 1
2O
3Hydrobon catalyst powder 20.0g, with 40ml, contain basic nickel carbonate 0.25wt% and contain the ammonium metatungstate of ammonium metatungstate 2.0wt%-basic carbonate nickel solution and soak, add 1.6g after 120 ℃ of oven dry and be used to prepare the gamma-aluminium oxide carrier of this kind Hydrobon catalyst (specific area is 319m
2/ g, pore volume are 0.65cm
3/ g, average pore size is 8.2nm) and porphyrize to 250 order, add the moulding of 4.5g bonding agent.Then under the condition identical with embodiment 1 to catalyst regeneration.The gained catalyst be numbered E.
Comparative example 1
The useless W-Ni/Al that uses among the embodiment 1
2O
3Hydrobon catalyst powder 20.0g adds the moulding of 4.5g bonding agent.Then under the condition identical with embodiment 1 to catalyst regeneration.The gained catalyst be numbered F.
Embodiment 1～5, and the physical and chemical performance and the activity rating result that obtain catalyst in the comparative example 1 all see Table 1.
As can be seen from Table 1, if the relative activity with the catalyst that obtains in the comparative example 1 is a benchmark, in dead catalyst, add reactive metal and salic material after regeneration, reactive metal state of aggregation species do not appear in catalyst surface, acidity and pore structure are improved significantly, and activity has significant increase.
Obtain the physical and chemical performance and the activity rating result of catalyst in table 1 embodiment 1～5 and the Comparative Examples 1
| The catalyst numbering | A | B | C | D | E | F |
| Physico-chemical property: specific area, m 2/ g pore volume, cm 3/ g average pore size, the nm total acid, mmol/g B acid, mmol/g L acid, mmol/g thing phase HDS relative activity, % | 108.3 0.18 6.53 0.183 0.129 0.054 γ-Al 2O 3 117 | 124.6 0.20 6.47 0.190 0.127 0.063 γ-Al 2O 3 109 | 115.3 0.19 6.50 0.182 0.123 0.059 γ-Al 2O 3 118 | 105.8 0.17 6.55 0.179 0.119 0.060 γ-Al 2O 3 120 | 117.3 0.19 6.38 0.191 0.128 0.063 γ-Al 2O 3 125 | 98.4 0.15 6.25 0.135 0.104 0.031 γ-Al 2O 3 100 |
Embodiment 6
Getting a kind of granularity is MoCo/Al useless about 140 orders
2O
3The hydrodenitrogenation catalyst powder (contains 18.46wt%MoO
3, 3.54wt%CoO, 11.30wt%C, 4.71wt%S, 0.05wt%Fe, surplus is Al
2O
3) 20g, with 40ml, contain basic cobaltous carbonate 0.1wt%, contain cobalt nitrate 0.1wt% and contain metamolybdic acid ammonium-basic cobaltous carbonate of metamolybdic acid ammonium 0.8wt%-cobalt nitrate solution and soak, (specific area is 319m to add the 0.9g gamma-aluminium oxide carrier after 120 ℃ of oven dry
2/ g, pore volume are 0.65cm
3/ g, average pore size is 8.2nm) porphyrize to 140 order, add the moulding of 3.1g bonding agent again.Under the following conditions this catalyst is regenerated then: with the catalyst regenerating unit of packing into, with nitrogen device is replaced earlier, then oxygen content is transferred to 1.0v% and heat 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 regenerated catalyst be numbered G.
Embodiment 7
Get the useless MoCo/Al that uses among the embodiment 6
2O
3Hydrodenitrogenation catalyst powder 20.0g adds 0.36gNiO and 1.85gWO
3, (specific area is 319m to add the gama-alumina that granularity is 140 purpose 6.25g again
2/ g, pore volume are 0.65cm
3/ g, average pore size is 8.2nm), and mixing, add the moulding of 8.2g bonding agent again.Then under the condition identical with embodiment 1 to catalyst regeneration.The gained catalyst be numbered H.
Comparative example 2
The useless WNi/Al that uses among the embodiment 6
2O
3Hydrobon catalyst powder 20.0g adds the moulding of 4.5g bonding agent.Then under the condition identical with embodiment 6 to catalyst regeneration.The gained catalyst be numbered I.
Embodiment 6,7, and the physical and chemical performance and the activity rating result that obtain catalyst in the comparative example 2 all see Table 2.
Obtain the physical and chemical performance and the activity rating result of catalyst in table 2 embodiment 6,7 and the comparative example 2
| The catalyst numbering | G | H | I |
| Physico-chemical property: specific area, m 2/ g pore volume, cm 3/ g average pore size, the nm total acid, mmol/g B acid, mmol/g L acid, mmol/g thing phase HDN relative activity, % | 101.0 0.16 6.31 0.149 0.111 0.038 γ-Al 2O 3 105 | 195.3 0.36 7.50 0.320 0.225 0.095 γ-Al 2O 3 136 | 86.4 0.11 5.23 0.121 0.095 0.026 γ-Al 2O 3 100 |
As can be seen from Table 2, use with embodiment 1～5 granularity different catalysts powder, the reactive metal, salic material and the binding agent that add different content, change regeneration condition under, its activity of catalyst of handling with the method still has raising in various degree.
Claims (10)
1, a kind ofly prepare the method for Hydrobon catalyst, may further comprise the steps by useless Hydrobon catalyst:
A, useless Hydrobon catalyst are ground to 100～400 orders;
B, the salic material that adding simultaneously is used to prepare the reactive metal oxides or the reactive metal salt of Hydrobon catalyst and is used to prepare hydrogenation catalyst in the powder that steps A obtains;
C, in the powder that step B obtains, add bonding agent, it is mixed pinch, moulding;
The processing of regenerating of D, the article shaped that the C step is obtained;
The described regeneration of step D is treated to: with the gas that contains oxygen 0.5v%～10.0v% article shaped is carried out the substep coke-burning regeneration in regenerating unit, divide four-stage to carry out, the condition in each stage is: at 100～140 ℃ of constant temperature 1～3h, at 150～240 ℃ of constant temperature 1～3h, at 250～350 ℃ of constant temperature 1～2h, at 450～550 ℃ of constant temperature 2～4h.
2, method according to claim 1, the Hydrobon catalyst that it is characterized in that will giving up in the steps A is ground to 200～300 orders.
3, method according to claim 1 is characterized in that reactive metal in reactive metal oxides described in the step B or the reactive metal salt is one or more in molybdenum, tungsten, cobalt and the nickel.
4,, it is characterized in that the reactive metal described in the step B selects one or more bimetallics among Mo-Co, Mo-Ni, W-Co and the W-Ni for use according to claim 1 or 3 described methods.
5, method according to claim 1 is characterized in that the reactive metal described in the step B selects the reactive metal identical with the kind of the used metal of raw catalyst for use.
6,, it is characterized in that the reactive metal amount that is added among the step B accounts for the 1wt%～80wt% of reactive metal total amount on the dead catalyst according to claim 1 or 3 described methods.
7,, it is characterized in that the reactive metal amount that is added among the step B accounts for the 2wt%～30wt% of reactive metal total amount on the dead catalyst according to claim 1 or 3 described methods.
8, method according to claim 1 is characterized in that the salic material that being used to described in the step B prepare hydrogenation catalyst is alumina-based supports and/or hydrated alumina, and its granularity is 100～400 orders.
9, method according to claim 8 is characterized in that the alumina-based supports described in the step B is γ-Al
2O
3Perhaps one or more in the gama-alumina of titaniferous, silicon, zirconium, phosphorus or boron, wherein the content of gama-alumina in the gama-alumina of titaniferous, silicon, zirconium, phosphorus or boron is greater than 50wt%; Hydrated alumina is a water aluminium oxide and/or a boehmite.
10, method according to claim 1 is characterized in that the weight of the bonding agent that adds among the step C accounts for 10%～30% of the resultant substance weight of step B.
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| CN 03134001 CN1290617C (en) | 2003-09-15 | 2003-09-15 | Process for preparing hydrogenating refining catalyst by waste hydrogenating refining catalyst |
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|---|---|---|---|
| CN 03134001 CN1290617C (en) | 2003-09-15 | 2003-09-15 | Process for preparing hydrogenating refining catalyst by waste hydrogenating refining catalyst |
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| CN1290617C true CN1290617C (en) | 2006-12-20 |
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| CN103381374B (en) * | 2013-03-03 | 2015-11-11 | 曹学仁 | A kind of preparation method of catalyst protective agent filler |
| 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 |
| CN106795443B (en) | 2014-07-17 | 2022-05-13 | 沙特基础全球技术有限公司 | Upgrading hydrogen-depleted streams using hydrogen donor streams in hydropyrolysis processes |
| CN104368361B (en) * | 2014-09-22 | 2016-05-18 | 攀枝花市正源科技有限责任公司 | The low cost reclaiming method of discarded SCR catalyst and regeneration SCR catalyst carrier |
| CN106140185A (en) * | 2016-06-27 | 2016-11-23 | 北京华福工程有限公司 | Useless hydrogenation catalyst prepares method and the gained serosity thereof of suspension bed hydrogenation catalyst |
| CN106140168A (en) * | 2016-06-27 | 2016-11-23 | 北京华福工程有限公司 | The processing method of a kind of useless hydrogenation catalyst and the serosity prepared by described method |
| US10619110B2 (en) * | 2018-04-11 | 2020-04-14 | Saudi Arabian Oil Company | Hydrocracking and hydrotreating catalytic compositions comprising a zeolite and regenerated, spent catalyst and uses thereof |
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Granted publication date: 20061220 |
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| CX01 | Expiry of patent term |