CN100509634C - Use of cationic layered materials, compositions comprising these materials, and the preparation of cationic layered materials - Google Patents
Use of cationic layered materials, compositions comprising these materials, and the preparation of cationic layered materials Download PDFInfo
- Publication number
- CN100509634C CN100509634C CNB038150921A CN03815092A CN100509634C CN 100509634 C CN100509634 C CN 100509634C CN B038150921 A CNB038150921 A CN B038150921A CN 03815092 A CN03815092 A CN 03815092A CN 100509634 C CN100509634 C CN 100509634C
- Authority
- CN
- China
- Prior art keywords
- composition
- slurry
- metal
- layered materials
- clm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
Use of cationic layered materials in hydrocarbon conversion, purification, a nd synthesis processes, such as fluid catalytic cracking. Cationic layered materials are especially suitable for the reduction of Sox and Nox emissions and the reduction of the sulfur and nitrogen content in fuels like gasoline and diesel. A new process is provided for the preparation of cationic layere d materials, which process avoids the use of metal salts and does not require the formation of anionic clay as intermediate.
Description
The present invention relates to cationic layered materials new purposes, contain the preparation method of the composition and the cationic layered materials of these materials.
Cationic layered materials (CLM) is a kind of crystal NH with characteristic X-ray diffractogram
4-Me (II)-TM-O phase.In this structure, Me (II) represents divalent metal, and TM represents transition metal.The CLM structure is by divalent metal octrahedra and the tetrahedral negative charge layer of transition metal and be clipped in charge compensation cation composition between these layers.
The CLM structure is relevant with the structure of hydrotalcite and houghite material.These those skilled in the art are referred to as the material of layered double-hydroxide (LDH) or anionic clay again and are made up of Me (II)-Al oxyhydroxide and the commutative negatively charged ion that is in the interlayer.To term " anionic clay " is that hydrotalcite is similar with the synonym of houghite material, and " cationic clay " can be used as the synonym of CLM.
CLM is well known in the prior art.People such as M.P.Astier (Ann.Chim.Fr. the 12nd volume, 1987, the 337-343 pages or leaves) prepare CLM in the following way: at first Ammonium Heptamolybdate and nickelous nitrate are dissolved in the ammonia soln, change pH by vaporized ammonia subsequently, thereby cause precipitating action.After overaging, washing and drying, form pure crystal CLM with characteristic X-ray diffractogram.
US 6,156, and 695 have described the similar intermediate processing that is used to prepare the CLM that contains Ni, W and Mo.
D.Levin, S.Soled and J.Ying (Chem.Mater. the 8th volume, 1996, the 836-843 pages or leaves; ACS Symp.Ser. the 622nd volume, 1996, the 237-249 pages or leaves; Stud.Surf, Sci.Cabal. the 118th volume, 1998, the 359-367 pages or leaves) method for preparing CLM also disclosed.Their method comprises step: (a) precipitation divalent metal salt and aluminum nitrate, (b) make described throw out aging to form anionic clay, (c) calcine this anionic clay to form mixed oxide, with (d) thus this mixed oxide is contacted with Ammonium Heptamolybdate and reacts-remove aluminum ion and introduce molybdenum acid ion-result's formation and have the CLM of trace (for example 0.63 weight %) aluminium.
Have been found that now that CLM can transform at hydrocarbon, suitably be used in purification or synthesis technique, especially refining oil industry and the Fischer-Tropsch process (Fischer-Tropsh) or as catalyzer or catalyst additive.The example that wherein can suitably use the technology of CLM is the discharging of catalytic cracking, hydrogenation, dehydrogenation, hydrocracking, hydrotreatment (hydrodenitrification, hydrogenating desulfurization, hydrodemetallation (HDM)), polymerization, steam conversion, base catalyzed reactions, Fischer-Tropsch process and minimizing SOx and NOx.
CLM is specially adapted to FCC technology, especially as the FCC catalyzer or be used for the active material of the catalytic additive of following purpose: (i) reduce the nitrogen and/or the sulphur content of fuel such as gasoline and/or diesel oil and/or (ii) reduce the discharging of SOx and/or NOx.
Therefore, the present invention relates to the purposes of cationic layered materials in hydrocarbon conversion, purification or synthesis technique.This cationic layered materials can prepare according to the inventive method hereinafter described, or the art methods preparation for example mentioned above according to any other method.
The art methods of preparation CLM all uses water-soluble divalent metal salt and aluminium salt as parent material, and this is disadvantageous especially.
At first, these soluble metal salt are relatively more expensive.The second, these methods need precipitation process, for not being very tempting so that technical scale is implemented, repeat to filter and wash the very step of fine particle (gel-type) because this comprises.This method relates to large-scale production unit, low-down throughput and a large amount of contaminated waste water.The 3rd, the use of salt means the use negatively charged ion.These negatively charged ion must remove with filtration step by washing (this filtration problem that can produce above-mentioned relevant fine particulate materials with contain for example waste water materials flow of nitrate, vitriol, halogen etc.) or will be in drying or calcining step as dischargings such as the gas of hostile environment such as oxynitride, halogen, oxysulfides.
The present invention also provides a kind of method of using inexpensive feedstock production cationic layered materials.Particularly can avoid using metal-salt, thereby it is friendly especially and meet the method for the environmental restraint that commercial operation is increased day by day more to obtain a kind of environment.In addition, this method does not comprise precipitation process.In addition, in a kind of method embodiment, needn't form anionic clay as intermediate, thereby can simplify described method.
The inventive method comprises step:
A) preparation contain can not be water-soluble aluminum feedstock and the slurry of divalent metal raw material,
B) drying step a) slurry and calcine described exsiccant material forming calcined materials one time,
C) randomly the product of step b) is carried out rehydration to obtain anionic clay, calcines this anionic clay subsequently forming the secondary clacining material,
D) slurry with calcined materials or secondary clacining material contacts with the transition metal ammonium salt,
E) make the slurry of gained aging.
This method can comprise additional step, for example middle drying step, forming step, grinding steps, additional aging step, additional calcining step or washing and filtration step.In addition, if suitable, can add additional compound as acid, alkali or metallic compound.
In the first method embodiment, do not carry out step c), this means that the product with step b) contacts with the transition metal ammonium salt, i.e. step d).In this embodiment, although may in step a), form a small amount of anionic clay, can not form anionic clay as intermediate.
In the second method embodiment, form anionic clay as intermediate product by the material rehydration that step b) is obtained.
In aging step e), aluminium is removed from middle material.If if at the step e) after-filtration and wash described material and aging condition and make the aluminium that is removed not become soluble, so this aluminium will can not be present in the final product.But, if if unreal baptize to wash in step and/or the weathering process form insoluble aluminum compound, aluminium will for example aluminum oxide or aluminium hydroxide, metal aluminate or molybdic acid aluminium be present in the final composition as independent aluminum contained compound so.Will set forth as following, this independent aluminum contained compound can have some advantages.
Therefore, the invention still further relates to the composition that comprises CLM and aluminum oxide or aluminium hydroxide, metal aluminate or molybdic acid aluminium like this.
Aluminum feedstock that can not be water-soluble
What can be used for the inventive method can not comprise aluminum oxide and aluminium hydroxide by water-soluble aluminum feedstock, example gel aluminum oxide, boehmite, pseudobochmite (peptization or not peptization), aluminium trihydrate, the aluminium trihydrate of treated forms and their mixture.The example of aluminium trihydrate is crystalline aluminium trihydrate (ATH), for example the gibbsite that is provided by Reynolds Aluminium Company
Or JM
Level, BOC (bauxite mine enriched material), bayerite and promise gibbsite.BOC is the most inexpensive aluminum feedstock that can not be water-soluble.
Described aluminum feedstock that can not be water-soluble preferably has small grain size, preferably is lower than 10 microns.
By at 100-1,000 ℃ of following thermal treatment aluminium trihydrate (gibbsite) can easily obtain incinerating aluminium trihydrate in 15 minutes to 24 hours.In any case, for calcining temperature and the time that obtains incinerating aluminium trihydrate should be enough to make surface-area to compare remarkable increase with the surface-area of the gibbsite that obtains by Bayer process (bayer process), wherein said surface-area is generally 30-50m
2/ g.Within the scope of the present invention, incinerating aluminum oxide (Alcoa for example rapidly
Aluminum oxide) also is considered to a kind of through heat treated aluminium trihydrate.Rapidly the incinerating aluminum oxide by in special industry equipment at 800-1, in the very short time, handle the aluminium trihydrate under 000 ℃ and obtain, as US 4,051,072 and US 3,222,129 described.
Described aluminum feedstock that can not be water-soluble can mix up metallic compound, for example rare earth metal or transition metal.Example is the compound of for example Ce, La, V, Mg, Ni, Mo, W, Mn, Fe, Nb, Ga, Si, P, Bi, B, Ti, Zr, Cr, Zn, Cu, Co and their combination, and its amount is preferably 1-40 weight %.Needed metal depends on the Application Areas of final product.For example, for hydrotreatment, preferably Mo, Co, Ni, W, and use, preferably V, Ce, La, Ni, Zn, Fe, Cu, W, Mo for FCC.This mix up can not be water-soluble aluminum feedstock can obtain by any currently known methods of this area, for example with the compound of required metal to not heat-treating or hydrothermal process by water-soluble aluminum feedstock.Preferred oxide compound, oxyhydroxide and the carbonate that uses these metals, but also can use nitrate, hydrochloride, vitriol, phosphoric acid salt, acetate and oxalate.When with mix up can not be water-soluble aluminum feedstock when comprising the composition of CLM and aluminum oxide or aluminium hydroxide as starting material preparation, aluminum oxide that mixes up or aluminium hydroxide (controlled amounts) will be present in the final product.This will be of value to multiple application.
The divalent metal raw material
The divalent metal raw material that is applicable to the inventive method is for containing Zn
2+, Mn
2+, Co
2+, Ni
2+, Cu
2+, Fe
2+, Ca
2+, Ba
2+Compound and the mixture of described compound.Solid divalent metal raw material and soluble divalent metal raw material (for example nitrate, hydrochloride, acetate etc.) both is suitable for.Preferred oxide compound, oxyhydroxide, carbonate, subcarbonate, formate or the acetate of using.Also can use the divalent metal raw material combination.
Described divalent metal raw material can mix up metal such as Al, Ga, Cr, Fe, V, B, In, Nb, W, Mo, Ta or their mixture.This divalent metal raw material that mixes up can obtain by any currently known methods of this area, for example with the compound of required metal the divalent metal raw material is heat-treated or hydrothermal process.Preferred oxide compound, oxyhydroxide and the carbonate that uses these metals, but also can use nitrate, hydrochloride, vitriol, phosphoric acid salt, acetate and oxalate.
The transition metal ammonium salt
Described transition metal ammonium salt is preferably selected from Ammonium Heptamolybdate, ammonium tungstate, ammonium vanadate, ammonium dichromate, titanium acid ammonium and zirconic acid ammonium.Also can use these combination of compounds.
Processing condition
The inventive method can be carried out with intermittent mode or continuous mode, randomly carries out with the continuous steps operating method.The inventive method can also part intermittently and partial continuous carry out.
Described aluminum feedstock and divalent metal raw material that can not be water-soluble be added reactor and make its pulping in water.Can be by this reactors of heating such as any thermal source such as process furnace, microwave, infrared radiation source, heating jacket (electronics or have heating fluid), lamps.Described reactor can assemble agitator, baffle plate etc. to guarantee the described reactant of uniform mixing.
Aqeous suspension in the described reactor can obtain by water, divalent metal raw material and aluminum feedstock that can not be water-soluble are mixed with former state, slurry form or their array configuration.In addition, concerning water miscible divalent metal raw material, described divalent metal raw material can add with the solution form.Can adopt any interpolation order: described divalent metal raw material can be added in the slurry of described aluminum feedstock that can not be water-soluble, can can not add in the slurry or solution of described divalent metal raw material by water-soluble aluminum feedstock described, maybe described aluminum feedstock and divalent metal raw material that can not be water-soluble can be added in this reactor simultaneously.
Randomly, can pass through the mode of for example grinding, high shear mixing or kneading with the mixture of gained and/or independent material homogenizer.When using the raw metal of for example oxide compound, oxyhydroxide or carbonate, reasonably be to grind this raw metal usually particularly.Preferably, aluminum feedstock and divalent metal raw material (if can not be water-soluble) that can not be water-soluble be all ground.Even more preferably grind contain simultaneously can not be water-soluble aluminum feedstock and the slurry of divalent metal raw material.
If necessary, the organic or inorganic bronsted lowry acids and bases bronsted lowry can be infeeded described reactor or before infeeding reactor, the organic or inorganic bronsted lowry acids and bases bronsted lowry added the divalent metal raw material or aluminum feedstock that can not be water-soluble in, for example in order to control pH.Preferred pH regulator agent is an ammonium alkali, because harmful positively charged ion can not remain in the described product when dry like this.
Preferably avoid using the compound of alkali metal containing, this is because alkali-metal depositing is that some (catalysis) uses undesirable.
Randomly, can after step a), make described mixture ageing.Should aging can under envrionment conditions or near carrying out under the envrionment conditions, perhaps under heat condition or hydrothermal fluid condition, carry out.In this specification sheets scope, hydrothermal solution refer in the presence of the water (or steam) in being higher than under 100 ℃ and the elevated pressure (as autogenous pressure).Aging temperature can be in 20～400 ℃ scope.Preferred temperature range is 60～175 ℃.Suitable atmosphere comprises CO
2, N
2And air.Preferred atmosphere is an air.
In this aging step, can for example described aluminum feedstock be converted into other aluminum feedstocks with improved bonding properties.For example, the aluminium trihydrate can be converted into boehmite.
Should aging preferably not cause forming a large amount of anionic clays, because before step b), preferably the amount of the anionic clay of Xing Chenging is lower than 50 weight % of possible in theory anionic clay maximum, and wherein said possible in theory anionic clay maximum is can be by the amount that is present in the anionic clay that the amount of aluminum feedstock and divalent metal raw material forms in the described slurry.More preferably, before step b), form be lower than 30 weight %, more preferably less than 20 weight %, be more preferably and be lower than 10 weight % even more preferably less than the anionic clay of the described amount of 5 weight %.Most preferably, before carrying out step b), there is not anionic clay in the described slurry.
, 000 ℃, preferred 200-800 ℃, more preferably carry out under 400-600 ℃, most preferably about 450 ℃, carry out at 175-1 according to the calcining of step b).Described calcining can be carried out 15 minutes to 24 hours, and preferred 1～12 hour, most preferably 2～6 hours.The material of gained will be known as calcined materials one time.
According to second kind of embodiment, in aqeous suspension, a calcined materials (after randomly carrying out grinding steps) is carried out rehydration to obtain anionic clay.This rehydration can carried out under heat condition or the hydrothermal fluid condition and in the presence of the dissolved metal-salt, and wherein said metal-salt comprises nitrate, carbonate, vitriol, the oxalate of divalent metal (for example Zn, Mn, Co, Ni, Cu) or trivalent metal (for example Ga, Cr, Fe, V, Mo, W).
If carry out rehydration, so subsequently the anionic clay that obtains is calcined to obtain the secondary clacining material.Described secondary clacining is 150～1,000 ℃, preferred 200～800 ℃, more preferably carry out under 200～600 ℃, most preferably carries out about 450 ℃.Described calcining can be carried out 15 minutes to 24 hours, and preferred 1～12 hour, most preferably 2～6 hours.
Slurry with a calcined materials (referring to the first method embodiment) or secondary clacining material (referring to the second method embodiment) contacts with the transition metal ammonium salt then., the slurry of described calcined materials (after grinding steps randomly) is added in the slurry or solution of described metal-salt, perhaps vice versa for this reason.Also can handle the slurry of described calcined materials at elevated temperatures and add transition metal ammonium salt itself then or with the adding of its slurry or solution form.As selection, can prepare transition metal ammonium salt slurry or solution by other transistion metal compound (as oxide compound or oxyhydroxide) is added in the ammoniacal liquor.If have ammoniacal liquor in the described reactor, so can be by transistion metal compound is infeeded this reactor and described slurry of in-situ preparing or solution with solid, solution or slurry form.
Under 20～300 ℃, preferred 60～200 ℃, made described slurry aging 15 minutes to 24 hours, preferred 1～12 hour, more preferably 2～6 hours, stir simultaneously or do not stir, in the temperature of room temperature or rising with under barometric point or elevated pressure, carry out.Suitable atmosphere comprises CO
2, N
2Or air.Preferred atmosphere is an air.
In this aging step, from described material, aluminium is removed as dissolved substance.Selectively wash with filtration step and become the part of products therefrom to prevent the described aluminium of at least a portion.The product of Xing Chenging will mainly comprise the CLM of the x-ray diffraction pattern of the aforementioned CLM with acquisition such as the people that is similar to Astier like this.Mainly CLM is meant that this product can comprise and surpasses 50%, more preferably surpasses 70% CLM.
If in weathering process, do not form insoluble aluminum compound, can obtain to comprise the composition of CLM and aluminum contained compound so if do not wash with filtration step and/or by changing aging condition (for example improving pH and/or temperature).The type of aluminum contained compound will depend on aging condition.The example of this aluminum contained compound is aluminum oxide, oxyhydroxide or salt, and boehmite for example is as pseudobochmite or crystallite boehmite, bayerite, unbodied oxide compound or oxyhydroxide, metal aluminate or molybdic acid aluminium.
An importance of the inventive method is to have this aluminum contained compound in the final product.Aluminum contained compound is measured in these compositions and can be 1～50 weight %, is preferably 5～50 weight %.Described aluminum contained compound can be used as tackiness agent, produce porousness and high surface area, and introduces acidic site.Therefore, the composition of gained can be advantageously used for absorption agent or as catalyst additive or carrier.
Described aluminum contained compound can be a crystalline or unbodied, and has high surface area (〉 50m surely according to preparation condition
2) or low surface area (＜50m
2).For example, under hydrothermal fluid condition and the middle alkali that adds can form the composition that comprises CLM and crystallite boehmite with the aging operation that improves pH; Yet the aging operation under lesser temps and pressure can form the composition that comprises CLM and quasi-crystalline boehmites (being pseudobochmite).
In other embodiments, the present invention relates to comprise the composition of CLM and bivalent metallic compound (for example oxide compound or oxyhydroxide), and relate to the composition that comprises CLM and transistion metal compound.
The composition that comprises CLM and bivalent metallic compound can use aforesaid method by begin from excessive divalent metal raw material or weathering process from burnt product elimination part divalent metal prepare.The example of this composition is composition, CLM and the Zn (OH) of CLM and ZnO
2Composition and the composition of CLM, ZnO and (vacation) boehmite.
The composition that comprises CLM and transistion metal compound can use aforesaid method and adopt excessive transition metal ammonium salt preparation.
The invention still further relates to the compound compositions that comprises CLM and contain divalent metal, aluminium and/or transition metal.This examples for compounds is Zn-Mo title complex, Zinc aluminate, molybdic acid zinc-aluminium, Zn-Al anionic clay etc.
CLM that uses according to the present invention or the composition that contains CLM are generally the form of formed body.This forming operation can the preparation CLM or contain CLM composition during or carry out afterwards.For example, in aforesaid method, step a) can not be water-soluble aluminum feedstock and the slurry of divalent metal raw material can carry out calcining step b) moulding before, the anionic clay that forms in the step c) can moulding before calcining, and perhaps described material can be by carrying out this step and moulding during aging step e) in kneader (can heat).
Suitable forming method comprises spraying drying, granulation, extrudes that (randomly with mediate combine), Cheng Zhu or any other are used for the conventional forming method in catalyzer and absorption agent field or the combination of described method.The amount that is used for the slurry liquid of moulding should adapt with pending concrete forming step.Reasonably way is that (part) removed the liquid that uses in the described slurry and/or added additional or other liquid, but and/or changes the pH of precursor mixture so that described slurry gelation and thereby suitable moulding.The multiple additives (as extruding additive) that is generally used in the different forming methods can add the precursor mixture that is used for moulding.Can in described slurry, add other component, for example zeolite, clay, silica, aluminum oxide, phosphoric acid salt and other catalytically active material known in the art during this forming step.
Use for some, wish at CLM or contain in the composition of CLM and/or at CLM or contain on the composition of CLM and have additive.Suitable additive comprises oxide compound, oxyhydroxide, borate, zirconate, aluminate, sulfide, carbonate, nitrate, phosphoric acid salt, silicate, titanate and the halogenide of rare earth metal (for example Ce, La), Si, P, B, VI family, VIII family precious metal (for example Pt, Pd), alkaline-earth metal (for example Mg, Ca and Ba) and transition metal (for example W, V, Mn, Fe, Ti, Zr, Cu, Co, Ni, Zn, Mo, Sn).
Described additive can easily be deposited on CLM or contain on the composition of CLM.As selection, described additive can add in any step of aforesaid method.Described additive can for example add in the initial compounds, but also can add individually in any slurry of this method use.As selection, described additive can add before first calcining step or second calcining step just.Preferably, grind the slurry that contains described additive.
If desired, CLM or the composition that contains CLM can carry out ion-exchange.In ion exchange process, the charge balance cation of interlayer (is NH
4+) replaced by other positively charged ion.Suitable cationic example is Na
+, K
+, Al
3+, Ni
2+, Cu
2+, Fe
2+, Co
2+, Zn
2+, other transition metal, alkaline-earth metal and rare earth metal and column positively charged ion be as (pillaring cation) [Al
13]
7+The Keggin ion.In aforesaid method, described ion-exchange is carried out before or after can or containing the composition of CLM at dry CLM.
The inventive method also relates in essence the catalyst composition that (promptly irrelevant with the preparation method) comprises CLM or contain the composition of CLM.Described catalyst composition can comprise all components that is present in catalyst composition usually, for example for example metal oxide, sulfide, nitride, phosphoric acid salt, silicon-dioxide, aluminum oxide, (inflatable) clay, anionic clay, preovskites, titanium dioxide, titanium dioxide-aluminum oxide, zirconium white, spinel and silica-alumina of matrix and/or matrix material, zeolite (for example faujusite, pentasil type zeolite and β zeolite), binder component and additional phase.For for example hydrotreatment of special purposes, can carry out pre-treatment to CLM, for example sulfuration.
In the FCC catalyst composition, CLM be especially suitable for use as and remove SOx and/or NOx, catch metal and reduce gasoline and diesel oil fuel in N and/or the active ingredient of S content.
The catalyst composition that contains CLM can be by preparing making it other catalyst component be added CLM before being shaped to formed body or contain in the composition of CLM.As selection, described catalyst component can form the CLM of (and subsequent grinding) or contain the composition of CLM in slurry with formed body mixes.Then can be once more the mixture of gained be carried out forming operation.
CLM and the composition that contains CLM also can be with former state or formed body form and catalyst mix as compositions of additives.Therefore, the invention still further relates to the catalyst additive compositions that comprises CLM.These compositions of additives are particularly suitable in the FCC method as removing SOx and/or NOx, catch metal and reducing N in gasoline and the diesel oil fuel and/or the active ingredient of S content, especially when metal (as Ce and/or V) be present among the CLM or CLM on the time.
CLM can further calcine to form metal oxide composition with the composition that contains CLM.Described calcining can be 200～1,000 ℃, preferred 400～600 ℃, more preferably carry out under 450 ℃.Described metal oxide can cure, handle to produce reactive catalyst compositions by hydrogen, CO or the reduction of other reductive agent or to it, and described reactive catalyst compositions can be suitable as catalyzer or the catalyst additive that FCC, HPC, dehydrogenation and fischer-tropsch process are used.For example, by making described metal oxide and sulfocompound such as H
2S contacts and vulcanizes.Described sulfocompound can be used as gas by described metal oxide composition, and perhaps it may reside in the slurry that comprises described metal oxide composition.
As selection, this metal oxide composition can randomly carry out rehydration with formation CLM or contain the composition of CLM in aqueous solution neutralization in the presence of additive, and described CLM or the composition that contains CLM randomly comprise additive.
The accompanying drawing summary
Fig. 1 has shown the sulphur concentration in the FCC gasoline and the relation of hydrocarbon conversion rate for different cationic layered materials and two reference coupon.
Embodiment
Embodiment 1
In 130ml water, make 15.3g gibbsite and alkaline carbonic acid zinc ZnCO
32ZnOH
2The mixture pulping of O (Zn/Al atomic ratio 3:1).Grind this slurry.The slurry of dry gained was also calcined 4 hours down at 500 ℃ subsequently.Then this material (10g) is heated to 85 ℃ and aging all night, in the aqueous solution (550ml) of 0.042M Ammonium Heptamolybdate, stirs simultaneously.Filter and wash this product.According to powder x-ray diffraction figure, this product contains on the structure reports identical cationic layered materials with people such as M.P.Astier.
Use the ultimate analysis of SEM-EDAX to show that the Zn/Al atomic ratio in this product is 1.25.Therefore, this product is the composition of a kind of CLM of comprising and aluminum contained compound.
Embodiment 2
By under 120 ℃, pH4 (regulating pH) condition with HNO3 in zinc nitrate aqueous solution (10 weight %Zn
2+) in handle incinerating gibbsite (42.5g) 2 hours rapidly and preparation mixes up the pseudobochmite of Zn.This solid content of slurry is 20 weight %.The pseudobochmite (172g) that then this is mixed up Zn mixes with alkaline carbonic acid zinc (being enough to reach the Zn/Al atomic ratio is 2), makes its pulping (final solid content 22%) and grinding in water.Dry this slurry and 500 ℃ of following calcinings in place subsequently 4 hours.Aging all night described burnt product (10g) is stirring in 550ml 0.092M Ammoniun Heptamolybdate Solution under 85 ℃ simultaneously.The material that filter, washing obtains, and dry all night under 85 ℃.
According to powder x-ray diffraction figure, this product contains on the structure reports identical cationic layered materials with people such as M.P.Astier.
Embodiment 3
Make pulping in the mixture of 15.3g gibbsite, alkaline carbonic acid nickel and zinc subcarbonate at 285ml water.(Zn+Ni): the Al atomic ratio is 3:1, and Ni:Zn is than being 1:1.Grind this slurry.The slurry that drying obtains was also calcined 4 hours down at 500 ℃ subsequently.Then incinerating material (10g) is heated to 85 ℃ and aging all night, in the 0.042M Ammonium Heptamolybdate aqueous solution (550ml), stirs simultaneously.Filter and wash this product.According to powder x-ray diffraction figure, this product contains on the structure reports identical cationic layered materials with people such as M.P.Astier.
Embodiment 4
In water, make 21.3g Chattem
TMThe mixture pulping of unbodied gel alumina and 11.8g alkaline carbonic acid zinc (Zn:Al atomic ratio 3.0) (solid content 19 weight %), and in retort furnace, in air and under 500 ℃, calcined 4 hours subsequently.The products therefrom rehydration that in 1657ml1M yellow soda ash, makes 62.9g under 70 ℃ 3 days, and stir simultaneously.PXRD (powder x-ray diffraction) figure confirms to have formed the Zn-Al anionic clay with a small amount of ZnO.
The Zn-Al anionic clay of preparation was like this calcined 4 hours down in 400 ℃ in air.With calcinate (10g) pulping in 550ml 0.042M Ammoniun Heptamolybdate Solution, and stir simultaneously.Heating this mixture also mixes it then with incinerating Zn-Al anionic clay.Spend the night under 85 ℃ the slurry of gained being placed under the agitation condition, filter then, with deionized water wash and dry all night under 100 ℃.According to powder x-ray diffraction figure, this product contains on the structure reports identical cationic layered materials with people such as M.P.Astier.
Embodiment 5
Mixture pulping in 140ml water with 15.3g gibbsite and verdigris (the Cu:Al atomic ratio is 3:1).Grind this slurry.The slurry of dry gained was also calcined 4 hours down at 550 ℃ subsequently.Then the incinerating material is heated to 85 ℃ and aging all night, in the 0.042M Ammonium Heptamolybdate aqueous solution (550ml), stirs simultaneously.Filter and wash this product.According to powder x-ray diffraction figure, this product contains on the structure reports identical cationic layered materials with people such as M.P.Astier.
Use the ultimate analysis of SEM-EDAX to show that total mol ratio of Cu/Al is 2 in the main body product.Therefore, this product is the composition of a kind of CLM of comprising and aluminum contained compound.
Embodiment 6
With 10.6g incinerating gibbsite (Alcoa CP rapidly
Aluminum oxide) and mixture pulping (solid content 18.3 weight %) in water of 73.7g alkaline carbonic acid zinc (Zn:Al than for 3:1).100 ℃ down dry gained slurry and subsequently in retort furnace in air, 300 ℃ calcining 4 hours down.The products therefrom rehydration that in 2770ml1M yellow soda ash, makes 55.4g under 70 ℃ 3 days, and stir simultaneously.Filter, wash this product and dry down at 100 ℃.PXRD (powder x-ray diffraction) figure confirms to form the Zn-Al anionic clay of knowing clearly and having a small amount of ZnO.Filter, wash this product, and dry down at 100 ℃.PXRD (powder x-ray diffraction) collection of illustrative plates confirms to form the Zn-Al anionic clay of knowing clearly and having a small amount of ZnO.
The Zn-Al anionic clay of preparation was like this calcined 3 hours down in 500 ℃ in air.In 15.0g incinerating product, add the 150ml0.3M Ammoniun Heptamolybdate Solution.Heat this mixture to 85 ℃ and aging all night.Filter and with this product of deionized water wash, dry all night under 100 ℃.According to powder x-ray diffraction figure, this product contains on the structure reports identical cationic layered materials with people such as M.P.Astier.
Embodiment 7
The pulping in 335ml water with 22.9g gibbsite and alkaline carbonic acid zinc (Zn:Al is than being 3:1).Grind this slurry.The slurry of dry gained was also calcined 4 hours down at 500 ℃ subsequently.After the calcining, at 1MNa
2CO
3Under 65 ℃, make product rehydration 8 hours in the solution.Calcined this anionic clay 4 hours down at 400 ℃.
At room temperature aging all night then described incinerating product (10g) stirs in the 0.042M Ammonium Heptamolybdate aqueous solution (550ml) simultaneously.Direct 100 ℃ of down dry these products.According to powder x-ray diffraction figure, this product contains on the structure reports identical cationic layered materials with people such as M.P.Astier.
Embodiment 8
With 15.3g gibbsite and alkaline carbonic acid zinc ZnCO
32ZnOH
2Mixture pulping in 250ml water of O (Zn/Al atomic ratio 3:1) and 12 weight % cerous nitrates, wherein said 12 weight % cerous nitrates are according to CeO
2Total weight based on desciccate.Grind this slurry.The slurry of dry gained was also calcined 4 hours down at 500 ℃ subsequently.Then this material (10g) is heated to 85 ℃ and aging all night, in the aqueous solution (550ml) of 0.042M Ammonium Heptamolybdate, stirs simultaneously.Filter and with this product of deionized water wash, dry all night under 100 ℃.
Products therefrom is the cationic layered materials that contains Ce.
Embodiment 9
With 15.3g gibbsite and alkaline carbonic acid zinc ZnCO
32ZnOH
2Mixture pulping in 250ml water of O (Zn/Al atomic ratio 3:1) and 4 weight % ammonium meta-vanadates, wherein said 4 weight % ammonium meta-vanadates are according to V
2O
5(wherein, % is based on Al based on the total weight of desciccate
2O
3Dry gross weight with ZnO).Grind this slurry.The slurry of dry gained was also calcined 4 hours down at 500 ℃ subsequently.Then this material (10g) is heated to 85 ℃ and aging all night, in the aqueous solution (550ml) of 0.042M Ammonium Heptamolybdate, stirs simultaneously.Filter and with this product of deionized water wash, and dry all night under 100 ℃.
The product of gained is the cationic layered materials that contains V.
Embodiment 10
With 15.3g gibbsite, alkaline carbonic acid zinc ZnCO
32ZnOH
2Mixture pulping in 300ml water of O (Zn/Al atomic ratio 3:1), 12 weight % cerous nitrates and 4 weight % ammonium meta-vanadates, wherein said 12 weight % cerous nitrates and 4 weight % ammonium meta-vanadates are all according to the total weight of oxide-base in desciccate.Grind this slurry.The slurry of dry gained was also calcined 4 hours down at 500 ℃ subsequently.Then this material (10g) is heated to 85 ℃ and aging all night, in the aqueous solution (550ml) of 0.042M Ammonium Heptamolybdate, stirs simultaneously.Filter and with this product of deionized water wash, and dry all night under 100 ℃.
The product of gained is the cationic layered materials that contains Ce and V.
Embodiment 11
With 15.3g gibbsite and alkaline carbonic acid zinc ZnCO
32ZnOH
2Mixture pulping in 130ml water of O (Zn/Al atomic ratio 3:1).Grind this slurry.The slurry of dry gained was also calcined 4 hours down at 500 ℃ subsequently.Then this material (10g) is heated to 85 ℃ and aging all night, in the aqueous solution (550ml) of 0.042M Ammonium Heptamolybdate, stirs simultaneously.Filter and with this product of deionized water wash, and dry all night under 100 ℃.Make this product pulping in 150ml contains the solution of 12 weight % cerous nitrates, wherein said cerous nitrate is according to CeO
2Weight based on desciccate is calculated.The slurry of dry gained under 100 ℃.
Final product is the CLM of dipping cerium.
Embodiment 12
With 15.3g gibbsite and alkaline carbonic acid zinc ZnCO
32ZnOH
2Mixture pulping in 130ml water of O (Zn/Al atomic ratio 3:1).Grind this slurry.The slurry of dry gained was also calcined 4 hours down at 500 ℃ subsequently.Then this material (10g) is heated to 85 ℃ and aging all night, in the aqueous solution (550ml) of 0.042M Ammonium Heptamolybdate, stirs simultaneously.Filter and with this product of deionized water wash, and dry all night under 100 ℃.Make this product pulping in 150ml contains the solution of 4 weight % ammonium meta-vanadates, wherein said 4 weight % ammonium meta-vanadates are according to V
2O
5Weight based on desciccate is calculated.The slurry of dry gained under 100 ℃.
Final product is the CLM of vanadium impregnated.
Embodiment 13
With 15.3g gibbsite and alkaline carbonic acid zinc ZnCO
32ZnOH
2Mixture pulping in 130ml water of O (Zn/Al atomic ratio 3:1).Grind this slurry.The slurry of dry gained was also calcined 4 hours down at 500 ℃ subsequently.Then this material (10g) is heated to 85 ℃ and aging all night, in the aqueous solution (550ml) of 0.042M Ammonium Heptamolybdate, stirs simultaneously.Filter and with this product of deionized water wash, and dry all night under 100 ℃.Contain in the solution of 12 weight % cerous nitrates and the solution that 150ml contains 4 weight % ammonium meta-vanadates in 150ml and to make this product pulping, wherein said two kinds of concentration are all calculated in the weight of desciccate according to oxide-base.The slurry of dry gained under 100 ℃.
Final product is the CLM of dipping cerium and vanadium.
Embodiment 14
Mixture pulping in 200ml water with 19.9g gibbsite, alkaline carbonic acid nickel and zinc subcarbonate.(Zn+Ni): the Al ratio is 3:1, and Ni:Zn is than being 3:7.Grind this slurry.The slurry that drying obtains was also calcined 4 hours down at 550 ℃ subsequently.Then incinerating product (10g) is heated to 85 ℃ and aging all night, in the aqueous solution (550ml) of 0.042M Ammonium Heptamolybdate, stirs simultaneously.Filter and wash this product.
According to powder x-ray diffraction figure, this product contains on the structure reports identical cationic layered materials with people such as M.P.Astier.Use the ultimate analysis of SEM-EDAX to show and have aluminum compound in the product.
Embodiment 15
Mixture pulping in 285ml water with 15.3g gibbsite, verdigris and zinc subcarbonate.(Zn+Cu): the Al atomic ratio is 3:1, and Zn:Cu is than being 1:1.Grind this slurry.The slurry that drying obtains was also calcined 4 hours down at 500 ℃ subsequently.Then incinerating material (15g) is heated to 85 ℃ and aging all night, in the aqueous solution (150ml) of 0.3M Ammonium Heptamolybdate, stirs simultaneously.Filter and with this product of deionized water wash, and dry all night under 100 ℃.According to the powder x-ray diffraction collection of illustrative plates, this product contains on the structure reports identical cationic layered materials with people such as M.P.Astier.
Embodiment 16
With 2.0g gibbsite, alkaline carbonic acid zinc ZnCO
32ZnOH
2Mixture pulping in 160ml water of O (Zn/Al atomic ratio 10:1).Grind this slurry.The slurry that drying obtains was also calcined 4 hours down at 500 ℃ subsequently.Then described material (15g) is heated to 85 ℃ and aging all night, in the aqueous solution (150ml) of 0.3M Ammonium Heptamolybdate, stirs simultaneously.Filter and with this product of deionized water wash, and dry all night under 100 ℃.According to powder x-ray diffraction figure, this product contains on the structure reports identical cationic layered materials with people such as M.P.Astier.
Embodiment 17
Utilization exists
Ind.Eng.Chem.Res.The 27th volume (1988), thermographimetric method of testing test implementation example 1,2,7 that the 1356-1360 page or leaf is described and 14 product take off SOx in the FCC process ability.The commercialization of use standard is taken off SOx additive (REF) as a reference.
In nitrogen and 700 ℃ heating 30mg product sample 30 minutes down.Then, be that 200ml/min contains 0.32%SO with flow velocity
2, 2.0%O
2With surplus N
2Gas replace nitrogen.After 30 minutes, replace this to contain SO with nitrogen
2Gas and reduce the temperature to 650 ℃.After 15 minutes, use pure H
2Replace nitrogen and kept this condition 20 minutes.Repeat this circulation 3 times.The SOx absorbed dose of measurement sample in the hydrogen treatment process and burst size are as the changes in weight (%) of sample.
Table 1 has provided SOx absorbed dose and burst size in the 3rd circulation.This table has also shown efficiency ratio, and described efficiency ratio is defined as the ratio of SOx burst size and SOx absorbed dose.The ideal efficiency ratio is 1, and absorbed all SOx of this meaning discharge once more, thereby make catalyst life longer.
Table 1
| Sample | The absorption of oxysulfide (the weight % of raising) | The release of oxysulfide (the weight % of decline) | Efficiency ratio |
| Embodiment 1 | 3.06 | 2.37 | 0.77 |
| Embodiment 2 | 2.75 | 2.00 | 0.73 |
| Embodiment 7 | 2.09 | 1.04 | 0.50 |
| Embodiment 14 | 4.46 | 3.69 | 0.83 |
| Reference | 4.89 | 1.51 | 0.31 |
This shows to show that the efficiency ratio of sample of the present invention is higher than normal business desulfurization oxide addition.
Embodiment 18
Test implementation example 1,2,15 and 16 product reduce the ability of the sulphur content of FCC gasoline.
Calcined sample to be tested 2 hours.Then with burnt sample and commercial FCC catalyst mix; This mixture comprises required sample of 20 weight % and 80 weight %FCC catalyzer.
Use cracking temperature is that 550 ℃ the conventional FCC raw material that contains 2.9 weight % sulphur is gone up the described mixture of test at fixed-bed pilot plant (MST).In following three different catalysts: the sulphur content of measuring gasoline under the steam oil ratio (SOR): 2.5,3.5 and 4.5.
Test two seed ginsengs examination sample:
Reference coupon A:100% standard E-cat
Reference coupon B: contain the commercial FCC additive that 20 weight % are used to reduce the sulphur content of gasoline.
Fig. 1 shown three catalyzer and oil than under the relation of transformation efficiency of the sulphur content of gasoline and test sample.Obviously, described cationic layered materials can reduce the sulphur content in the gasoline.
Embodiment 19
Test implementation example 3,5,7 and 15 the take off NOx ability of product in the FCC process.These samples demonstrate the good NOx ability of taking off.
Claims (30)
1. method by aluminum feedstock and divalent metal feedstock production cationic layered materials, wherein the method comprising the steps of:
A) preparation contain can not be water-soluble aluminum feedstock and the slurry of divalent metal raw material,
B) drying step a) slurry and calcine described exsiccant material forming calcined materials one time,
C) product to step b) carries out rehydration to obtain anionic clay, and calcine this anionic clay subsequently with formation secondary clacining material, or do not carry out step c),
D) slurry of calcined materials or secondary clacining material is contacted with the transition metal ammonium salt and
E) make the slurry of gained aging.
2. the method for claim 1, wherein the slurry to step a) wears out before carrying out step b).
3. the method for claim 1 is wherein filtered and washing step e) product.
4. the method for claim 1 wherein in step b), made the exsiccant sizing material forming before calcining.
5. the method for claim 1 wherein made the anionic clay moulding that obtains in the step c) before calcining.
6. the method for claim 1 wherein can not be selected from alumina gel, boehmite, pseudobochmite, aluminium trihydrate and their mixture by water-soluble aluminum feedstock.
7. method as claimed in claim 6, the aluminium trihydrate that wherein said aluminium trihydrate is a treated forms.
8. the method for claim 1, at least a metallic compound wherein can not water-soluble aluminum feedstock mixes.
9. the method for claim 1, wherein said divalent metal raw material is Zn
2+, Mn
2+, Co
2+, Ni
2+, Fe
2+Or Cu
2+Oxide compound, oxyhydroxide, subcarbonate, carbonate, formate or acetate or their combination.
10. the method for claim 1, wherein said transition metal ammonium salt is the transition metal ammonium salt that is selected from Ammonium Heptamolybdate, ammonium tungstate, ammonium vanadate or ammonium dichromate and their combination.
11. the method for claim 1, wherein drying step e) product and at 200～1000 ℃ of following desciccates of calcining gained.
12. method as claimed in claim 11 wherein makes described calcinate rehydration in the presence of additive.
13. a composition, it comprises cationic layered materials and bivalent metallic compound by the method preparation of claim 1.
14. composition as claimed in claim 13, wherein said composition comprise one or more and are selected from following additive: oxide compound, oxyhydroxide, borate, zirconate, aluminate, sulfide, carbonate, nitrate, phosphoric acid salt, silicate, titanate and the halogenide of rare earth metal, Si, P, B, VI family metal, alkaline-earth metal and transition metal.
15. composition as claimed in claim 14, wherein said transition metal are VIII family precious metals.
16. comprise FCC catalyst composition by the cationic layered materials of the described method preparation of claim 1.
17. comprise FCC catalyst additive compositions by the cationic layered materials of the described method preparation of claim 1.
18. conversion, purification or a synthetic method that is used for hydrocarbon wherein makes the described cationic layered materials of hydrocarbon and claim 12 contact under hydrocarbon conversion, purification or synthesis condition.
19. method as claimed in claim 18, wherein said method are hydrodesulfurization, hydrodenitrification technology, fluid catalytic cracking or Fischer-Tropsch process.
20. method as claimed in claim 19, wherein said method are to be used to reduce the nitrogen content of fuel and/or the fluidized catalytic cracking method of sulphur content.
21. method as claimed in claim 20, wherein said fuel comprises gasoline and/or diesel oil.
22. method as claimed in claim 18, wherein said method make SOx and/or NOx discharging reduce.
23. a composition, the cationic layered materials that it comprises the method preparation by claim 1 comprises aluminum oxide, aluminium hydroxide, metal aluminate or the molybdic acid aluminium of 1-50 weight % in the described composition.
24. composition as claimed in claim 23, the rare-earth metal doped or transition metal of wherein said aluminum oxide or aluminium hydroxide.
25. composition as claimed in claim 23, wherein said composition comprise one or more and are selected from following additive: oxide compound, oxyhydroxide, borate, zirconate, aluminate, sulfide, carbonate, nitrate, phosphoric acid salt, silicate, titanate and the halogenide of rare earth metal, Si, P, B, VI family metal, alkaline-earth metal and transition metal.
26. composition as claimed in claim 25, wherein said transition metal are VIII family precious metals.
27. comprise FCC catalyst composition by the cationic layered materials of the described method preparation of claim 1.
28. comprise FCC catalyst additive compositions by the cationic layered materials of the described method preparation of claim 1.
29. the formed body that method according to claim 5 obtains.
30. the formed body that method according to claim 4 obtains.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US39104502P | 2002-06-25 | 2002-06-25 | |
| US60/391,045 | 2002-06-25 | ||
| EP02078429.4 | 2002-08-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1692077A CN1692077A (en) | 2005-11-02 |
| CN100509634C true CN100509634C (en) | 2009-07-08 |
Family
ID=35346939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038150921A Expired - Fee Related CN100509634C (en) | 2002-06-25 | 2003-06-24 | Use of cationic layered materials, compositions comprising these materials, and the preparation of cationic layered materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100509634C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8409428B2 (en) * | 2006-06-28 | 2013-04-02 | Saudi Arabian Oil Company | Catalyst additive for reduction of sulfur in catalytically cracked gasoline |
| EP2134651B1 (en) * | 2007-03-20 | 2018-02-14 | Albemarle Netherlands BV | Additive-containing anionic clays for reducing sox emissions from an fcc regenerator and process for making them |
| WO2009039095A2 (en) * | 2007-09-20 | 2009-03-26 | Shepherd Color Company | Non-chromate corrosion inhibitor formulas based on highly crystalline hydrotalcite analogs |
-
2003
- 2003-06-24 CN CNB038150921A patent/CN100509634C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1692077A (en) | 2005-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1205147C (en) | Attrition resistant, shaped, crystalline anionic clay-containing bodies | |
| EP1608464B1 (en) | Preparation of a catalyst composition and its use | |
| US7208446B2 (en) | Quasi-crystalline boehmites containing additives | |
| EP2691172B1 (en) | Mixed oxides of transition metals and preparation process | |
| EP1601457B1 (en) | Composition comprising a metal hydroxy salt, its preparation and use as catalyst or sorbent | |
| EP0999893A1 (en) | Nickel molybdotungstate hydrotreating catalysts | |
| AU2006308165A1 (en) | Bulk hydroprocessing catalyst comprising a group VIII metal and molybdenum, preparation and use thereof | |
| CN101432071A (en) | Hydrocracking catalyst comprising an in situ produced Y-fauajasite and hydrocracking process | |
| CN100542958C (en) | The preparation method who contains the anionic clay of additive | |
| JP2001104790A (en) | Catalyst for hydrogenation treatment and method for hydrogenation treatment of hydrocarbon oil using it | |
| CN101255359A (en) | Process for the hydroconversion in a slurry of heavy hydrocarbonaceous feedstocks in the presence of a dispersed phase and an alumina-based oxide | |
| JP4276622B2 (en) | Method for using cationic layered substance, composition containing these substances, and method for producing cationic layered substance | |
| EP0309046B1 (en) | Hydrotreating catalysts from hydrogels, process for their preparation and use | |
| CN100509634C (en) | Use of cationic layered materials, compositions comprising these materials, and the preparation of cationic layered materials | |
| US6716785B2 (en) | Composite and process for the in-situ preparation of a composite comprising a cationic clay and binder/matrix material | |
| AU602794B2 (en) | Process for the preparation of hydrotreating catalysts from hydrogels | |
| JP3784852B2 (en) | Refractory inorganic oxide catalyst carrier and hydrotreating catalyst using the carrier | |
| JP2007500593A (en) | Metal-containing compositions and their use as catalyst compositions | |
| US4880526A (en) | Hydrotreating catalysts prepared from hydrogels | |
| US7598202B2 (en) | Use of cationic layered materials, compositions comprising these materials, and the preparation of cationic layered materials | |
| US4810687A (en) | Hydrotreating catalysts prepared from hydrogels | |
| US4810684A (en) | Hydrotreating catalysts prepared from hydrogels | |
| US4880525A (en) | Process for hydrotreating hydrocarbon feeds | |
| US4820680A (en) | Hydrotreating catalysts prepared from hydrogels | |
| CN101687660A (en) | Additive-containing anionic clays for reducing sox emissions from an fcc regenerator and process for making them |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20051028 Address after: Holland Arnhem Applicant after: Akzo Nobel N. V. Co-applicant after: Albemarle Netherlands B. V. Address before: Holland Arnhem Applicant before: Akzo Nobel N. V. |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: ALBEMARLE NETHERLANDS B V Free format text: FORMER OWNER: AKZO NOBEL N.V.; APPLICANT Effective date: 20060714 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20060714 Address after: Amersfoort Holland Applicant after: Albemarle Netherlands B. V. Address before: Holland Arnhem Applicant before: Akzo Nobel N. V. Co-applicant before: Albemarle Netherlands B. V. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090708 Termination date: 20110624 |