Mixed oxides of transition metals, hydrotreatment catalysts obtained therefrom, and preparation process comprising sol-gel processes
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
B01J-031/00
B01J-023/00
B01J-027/051
B01J-027/049
B01J-035/10
B01J-037/03
B01J-037/20
C10G-045/08
B01J-023/883
B01J-023/888
B01J-021/00
B01J-025/00
출원번호
US-0969747
(2015-12-15)
등록번호
US-9975112
(2018-05-22)
우선권정보
IT-MI2009A1680 (2009-09-30)
발명자
/ 주소
Bellussi, Giuseppe
Carati, Angela
Gagliardi, Maria Federica
Zanardi, Stefano
Marella, Marcello
Scattolin, Roberto
Tomaselli, Michele
출원인 / 주소
ENI S.P.A.
대리인 / 주소
Oblon, McClelland, Maier & Neustadt, L.L.P.
인용정보
피인용 횟수 :
0인용 특허 :
5
초록▼
New sulfided metal catalysts are described, containing a metal X selected from Ni, Co and mixtures thereof, a metal Y selected from Mo, W and mixtures thereof, an element Z selected from Si, Al and mixtures thereof, and possibly an organic residue, obtained by the sulfidation of mixed oxide precurso
New sulfided metal catalysts are described, containing a metal X selected from Ni, Co and mixtures thereof, a metal Y selected from Mo, W and mixtures thereof, an element Z selected from Si, Al and mixtures thereof, and possibly an organic residue, obtained by the sulfidation of mixed oxide precursors, also new, having general formula (A) XaYbZcOd.pC (A)possibly shaped without a binder, or by sulfidation of mixed oxides having formula (A), in shaped form with a binder,wherein X is selected from Ni, Co and mixtures thereof,Y is selected from Mo, W and mixtures thereof,Z is selected from Si, Al and mixtures thereof,O is oxygen,C is selected from: a nitrogenated compound N,an organic residue deriving from the partial calcination of the nitrogenated compound N,said nitrogenated compound N, when present, being selected from:a) an alkyl ammonium hydroxide having formula (I) RIRIIRIIIRIVNOH (I)wherein the groups RIRIV, the same or different, are aliphatic groups containing from 1 to 7 carbon atoms,b) an amine having formula (II) R1R2R3N (II)wherein R1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, andR2 and R3, the same or different, are selected from H and a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl being equal to or different from R1,a, b, c, d are the number of moles of the elements X, Y, Z, O, respectively,p is the weight percentage of C with respect to the total weight of the precursor having formula (A),a, b, c, d are higher than 0a/b is higher than or equal to 0.3 and lower than or equal to 2,(a+b)/c is higher than or equal to 0.3 and lower than or equal to 10, preferably varying from 0.8 to 10d=(2a+6b+Hc)/2 wherein H=4 when Z=Si H=3 when Z=Aland p is higher than or equal to 0 and lower than or equal to 40%. Said catalysts can be used as hydrotreating catalysts.
대표청구항▼
1. A sol-gel process for preparing a mixed oxide of formula (A), comprising: preparing a hydroalcohol solution/suspension comprising at least one soluble or partially soluble source of at least one element X, at least one soluble or partially soluble source of at least one element Y, at least one so
1. A sol-gel process for preparing a mixed oxide of formula (A), comprising: preparing a hydroalcohol solution/suspension comprising at least one soluble or partially soluble source of at least one element X, at least one soluble or partially soluble source of at least one element Y, at least one soluble source, which can be hydrolyzed or dispersed, of at least one element Z and a nitrogenated compound N selected from:a) an alkyl ammonium hydroxide of formula (I) RIRIIRIIIRIVNOH (I)wherein RI, RII, RIII and RIV are the same or different and are aliphatic groups containing from 1 to 7 carbon atoms,b) an amine of formula (II) R1R2R3N (II)whereinR1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, andR2 and R3 are the same or different and are selected from H and a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl being equal to, or different from, R1;wherein the molar ratio N/(X+Y) is greater than 0.1 and less than, or equal to 1,obtaining the formation of a gel,maintaining the gel under stirring,maintaining the gel under static conditions,drying the gel prepared in the previous step, obtaining the mixed oxide precursor of formula (A2) XaYbZcOd.pC (A2)whereinX is selected from Ni, Co or a mixture thereof,Y is selected from Mo, W or a mixture thereof,Z is selected from Si, Al or a mixture thereof,O is oxygen,C is a nitrogenated compound N selected from the nitrogenated compounds mentioned above, having formula (I) or (II),a, b, c, d are the number of moles of the elements X, Y, Z and O, respectively,p is the weight percentage of C with respect to the total weight of the compound having formula (A2)a, b, c, d are greater than 0a/b is greater than or equal to 0.3 and less than or equal to 2,(a+b)/c is greater than or equal to 0.8 and less than or equal to 10 when Z is Si or a mixture of Si and Al, but is greater than or equal to 0.3 and less than or equal to 10 when Z is Al,d=(2a+6b+Hc)/2 wherein H=4 when Z=Si H=3 when Z=Aland p is greater than 0 and less than or equal to 40%, optionally subjecting the compound of formula (A2) resulting from the previous step, to partial or total calcination, respectively obtaining a compound having the same formula (A2) wherein C is an organic residue deriving from the calcination of the nitrogenated compound, or a mixed oxide of formula (A1) XaYbZcOd (A1)wherein X, Y, Z, O, a, b, c, d correspond to those of the previous formula (A2); andwherein said mixed oxide of formula (A) has the formula: XaYbZcOd.pC (A)whereinX is selected from Ni, Co or a mixture thereof,Y is selected from Mo, W or a mixture thereof,Z is selected from Si, Al or a mixture thereof,O is oxygenC is selected from: a nitrogenated compound N,an organic residue deriving from the nitrogenated compound N by partial calcination,wherein said nitrogenated compound N is selected from: a) an alkyl ammonium hydroxide of the formula (I) RIRIIRIIIRIVNOH (I)wherein the groups RI, RII, RIII and RIV are the same or different and are aliphatic groups containing from 1 to 7 carbon atoms,b) an amine having formula (II) R1R2R3N (II)whereinR1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, andR2 and R3 are the same or different and are selected from H and a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl being equal to or different from R1 a, b, c, d are the number of moles of the elements X, Y, Z, O, respectively,p is the weight percentage of C with respect to the total weight of the compound having formula (A),a, b, c, d are greater than 0a/b is greater than or equal to 0.3 and less than or equal to 2,(a+b)/c is greater than or equal to 0.8 and less than or equal to 10 when Z is Si or a mixture of Si and Al, but is greater than or equal to 0.3 and less than or equal to 10 when Z is Al,d=(2a+6b+Hc)/2 wherein H=4 when Z=Si H=3 when Z=Aland p is greater than or equal to 0 and less than or equal to 40%. 2. The process according to claim 1, wherein, when Z is silicon, the corresponding soluble compounds, which can be dispersed or hydrolyzed, are colloidal silica, fumed silica and tetraalkyl ortho silicates wherein the alkyl group contains from 1 to 4 carbon atoms. 3. The process according to claim 1, wherein, when Z is aluminium, the corresponding soluble compound is aluminium lactate and the corresponding dispersible or hydrolyzable compounds are dispersible aluminas, monohydrated aluminas AlOOH, trihydrated aluminas Al(OH)3, aluminium oxide, aluminium trialkoxides wherein the alkyl is linear or branched and can contain from 2 to 5 carbon atoms. 4. The process according to claim 1, wherein, in the last step, the total calcination is effected at a temperature of at least 450° C. 5. The process according to claim 4, wherein the total calcination is effected at a temperature higher than or equal to 450° C. and lower than or equal to 600° C. 6. The process according to claim 1, wherein the calcination is effected partially and at a temperature lower than 450° C. 7. The process according to claim 6, wherein the partial calcination is effected at a temperature ranging from 200 to 400° C. 8. The process according to claim 1, comprising the following steps: 1) an aqueous solution (a) is prepared of at least one soluble or partially soluble source of at least one metal Y, and alkyl ammonium hydroxide, of formula RIRIIRIIIRIVNOH (I)wherein the groups RI-RIV are the same or different and are aliphatic groups containing from 1 to 7 carbon atoms,is added to this solution,2) a solution/suspension (b) in alcohol is prepared, of a hydrolyzable or dispersible soluble compound of the element Z and of at least a soluble or partially soluble source of at least one metal X;3) the solution (a) and the solution/dispersion (b) are mixed, obtaining the formation of a gel;4) this gel is maintained under stirring,5) the gel is maintained under static conditions,6) the gel resulting from step (5) is dried, obtaining a mixed oxide of formula (A2) XaYbZcOd.pC (A2) wherein X is selected from Ni, Co or a mixture thereof,Y is selected from Mo, W or a mixture thereof,Z is selected from Si, Al or a mixture thereof,O is oxygen,C is a nitrogenated compound of formula (I),a, b, c, d are the number of moles of the elements X, Y, Z and O, respectively,p is the weight percentage of C with respect to the total weight of the compound of formula (A2)a, b, c, d are greater than 0a/b is greater than or equal to 0.3 and less than or equal to 2,(a+b)/c is greater than or equal to 0.8 and less than or equal to 10,d=(2a+6b+Hc)/2 wherein H=4 when Z=Si H=3 when Z=Alp is greater than 0 and less than or equal to 40%,7) the product obtained from step (6) is optionally subjected to partial or total calcination, obtaining, respectively, a compound having the same formula (A2) wherein C is an organic residue deriving from the calcination of the nitrogenated compound, or a mixed oxide of formula (A1): XaYbZcOd (A1) wherein X is selected from Ni, Co or a mixture thereof,Y is selected from Mo, W or a mixture thereof,Z is selected from Si, Al or a mixture thereof,O is oxygena, b, c, d are the number of moles of the elements X, Y, Z, O, respectively and are greater than 0a/b is greater than or equal to 0.3 and less or equal to 2,(a+b)/c is greater than or equal to 0.8 and less than or equal to 10d=(2a+6b+Hc)/2 wherein H=4 when Z=Si H=3 when Z=Al. 9. The process according to claim 8, wherein, in step (3), the ratios between the reagents, expressed as molar ratios of the elements, are the following: X/Y=0.3-2RIRIIRIIIRIVNOH/(X+Y)=0.1-0.6(X+Y)/Z is greater than or equal to 0.8 and less than or equal to 10 H2O/(X+Y+Z)>10Alcohol/H2O=0-1. 10. The process according to claim 9, wherein the following molar ratios between the elements in step (3) are used: X/Y=0.3-2RIRIIRIIIRIVNOH/(X+Y)=0.1-0.4(X+Y)/Z is greater than or equal to 0.8 and less than or equal to 10 H2O/(X+Y+Z)>10Alcohol/H2O=0.1-0.6. 11. The process according to claim 1, for preparing a compound of formula (A) wherein (Z) is silicon, comprising the following phases: a) a solution (C) is prepared in alcohol, of a hydrolyzable or dispersible compound of silicon, and an amine is also added to this solution, said amine having formula (II) R1R2R3N (II)whereinR1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, andR2 and R3 are the same or different and are selected from H and a linear, branched or cyclic alkyl containing from 4 to 12 carbon atoms, said alkyl being the same or different from RI;b) a solution/aqueous suspension (D) is prepared of at least one source of at least one metal X and of at least one source of at least one metal Y;c) the solution (C) and the solution/suspension (D) are stirred until a gel is formed;d) the gel is maintained under stirring,e) the gel is maintained under static conditions,f) the gel resulting from step (e) is dried, obtaining a mixed oxide precursor of formula (A2) XaYbZcOd.pC (A2)wherein X is selected from Ni, Co or a mixture thereof,Y is selected from Mo, W or a mixture thereof,Z is Si,O is oxygen,C is a nitrogenated compound having formula (II),a, b, c, d are the number of moles of the elements X, Y, Z and O, respectively,p is the weight percentage of C with respect to the total weight of the compound of formula (A2)a, b, c, d are greater than 0a/b is greater than or equal to 0.3 and less than or equal to 2,(a+b)/c is greater than or equal to 0.8 and less than or equal to 10,d=(2a+6b+Hc)/2 wherein H=4p is greater than 0 and less than or equal to 40%,g) the product obtained in the previous step is optionally subjected to partial or total calcination, obtaining, respectively, a mixed oxide having the same formula (A2) wherein C is an organic residue deriving from the partial calcination of the nitrogenated compound N, or a mixed oxide of formula (A1): XaYbZcOd (A1)wherein X is selected from Ni, Co or a mixture thereof,Y is selected from Mo, W or a mixture thereof,Z is SiO is oxygena, b, c, d are the number of moles of the elements X, Y, Z, O, respectivelya, b, c, d are greater than 0a/b is greater than or equal to 0.3 and less than or equal to 2,(a+b)/c is greater than or equal to 0.8 and less than or equal to 10,d=(2a+6b+Hc)/2 wherein H=4. 12. The process according to claim 11, wherein the following molar ratios between the elements of step (3) are used: X/Y=0.3-2R1R2R3N/(X+Y)=0.1-1(X+Y)/Si is greater than or equal to 0.8 and less than or equal to 10 H2O/(X+Y+Si)>10Alcohol/H2O=0-0.4. 13. The process according to claim 1, for preparing compounds having formula (A) wherein (Z) is aluminum, comprising the following phases: a) a solution (C) is prepared in alcohol, of an amine of formula (II) R1R2R3N (II)whereinR1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, andR2 and R3 are the same or different and are selected from H and a linear, branched or cyclic alkyl containing from 4 to 12 carbon atoms, said alkyl being the same or different from RI;b) a solution/aqueous suspension (D) is prepared of soluble or partially soluble sources of at least one metal X, at least one metal Y and a hydrolyzable compound of aluminum;c) the solution (C) and the solution/suspension (D) are mixed until a gel is formed;d) the gel is maintained under stirring,e) the gel is maintained under static conditions,f) the gel resulting from step (e) is dried, obtaining a precursor mixed oxide of formula (A2) XaYbZcOd.pC (A2)wherein X is selected from Ni, Co or a mixture thereof,Y is selected from Mo, W or a mixture thereof,Z is Al,O is oxygen,C is a nitrogenated compound of formula (II),a, b, c, d are the number of moles of the elements X, Y, Z and O, respectively,p is the weight percentage of C with respect to the total weight of the compound of formula (A2)a, b, c, d are greater than 0a/b is greater than or equal to 0.3 and less than or equal to 2,(a+b)/c is greater than or equal to 0.3 and less than or equal to 10,d=(2a+6b+Hc)/2 wherein H=3p is greater than 0 and less than or equal to 40%,g) the product obtained in the previous step is optionally subjected to partial or total calcination, obtaining, respectively, a mixed oxide having the same formula (A2) wherein C is an organic residue deriving from the partial calcination of the nitrogenated compound, or a mixed oxide of formula (A1): XaYbZcOd (A1)wherein X is selected from Ni, Co or a mixture thereof,Y is selected from Mo, W or a mixture thereof,Z is AlO is oxygena, b, c, d are the number of moles of the elements X, Y, Z, O, respectivelya, b, c, d are greater than 0a/b is greater than or equal to 0.3 and less than or equal to 2,(a+b)/c is greater than or equal to 0.3 and less than or equal to 10,d=(2a+6b+Hc)/2 wherein H=3. 14. The process according to claim 13, wherein, in phase (c), the ratios between the reagents, expressed as molar ratios between the elements, are the following: X/Y=0.3-2R1R2R3N/(X+Y)=0.1-1(X+Y)/Al is higher than or equal to 0.3 and lower than or equal to 10 H2O/(X+Y+Al)>10Alcohol/H2O=0-1.
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이 특허에 인용된 특허 (5)
Zanibelli, Laura; Ferrari, Marco; Arrigoni, Virginio, Catalytic composition for the upgrading of hydrocarbon mixtures.
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Halbert Thomas R. (Annandale NJ) Stiefel Edward I. (Bridgewater NJ) Chianelli Russell R. (Somerville NJ) Ho Teh C. (Bridgewater NJ), Promoted molybdenum and tungsten sulfide catalysts, their preparation and use.
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