# US 11,078,088 B2 · Highly active multimetallic materials using short-chain alkyl quaternary ammonium compounds

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- Number: US 11,078,088 B2
- Document ID: US11078088B2
- Status: Granted
- Kind: B2
- Application number: 16/206,898
- Filed: 2018-11-30
- Published: 2019-06-20
- Granted: 2021-08-03
- Earliest claimed: 2017-12-20
- Assignees: Uop LLC
- Applicants: Uop LLC
- Inventors: Zara Osman; Wei Pan
- Web page: https://patentgrep.com/patent/US11078088B2

## CPC

- C01G 53/40: Complex oxides containing nickel and at least one other metal element
- B01J 23/002: {Mixed oxides other than spinels, e.g. perovskite}
- B01J 23/8878: {Chromium}
- B01J 23/888: Tungsten
- C01G 1/02: Oxides
- B01J 35/70: characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00)
- B01J 35/80: characterised by their amorphous structures
- B01J 37/20: Sulfiding
- B01J 2235/15: X-ray diffraction
- B01J 2523/67: Chromium
- B01J 2523/68: Molybdenum
- B01J 2523/69: Tungsten
- B01J 2523/842: Iron
- B01J 2523/845: Cobalt
- B01J 2523/847: Nickel
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C10G 45/08: in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES

## Abstract

A highly active quaternary mixed transition metal oxide material has been developed. The material may be sulfided to generate metal sulfides which are used as a catalyst in a conversion process such as hydroprocessing. The hydroprocessing may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

## Claims

### Claim 1

A mixed transition metal oxide material having the formula:
(MIa)m(MIIb)n(MIIIc)oOeq
where:
MI is a metal or a mixture of metals selected from Group VIII (IUPAC Groups 8, 9, and 10);
MII is a metal selected from Group VIB (IUPAC Group 6);
MIII is a metal selected from Group VIB (IUPAC Group 6) which is different from MII;
a, b, c, and e are the valence state of MI, MII, MIII, and O;
m, n, o, and q are the mole ratio of MI, MII, MIII, and O, wherein m/(n+o) is from 1/10 to 10/1, wherein 0<n/o≤100 and 0≤o/n≤100, wherein q is greater than 0; and wherein a, b, c, e, m, n, o, and q satisfy the equation:
a*m+b*n+c*o+e*q=0
the material further characterized by an X-ray diffraction pattern comprising a broad peak between 2θ of 55° and 58° with the full width at half maximum larger than 3° and at least one of:
one or more sharp peaks between 2θ of 5° and 11.5° with the full width at half maximum less than 0.3°; and
one or more sharp peaks between 2θ of 11.5° and 32° with the full width at half maximum less than 0.6°.

### Claim 2 (depends on 1)

The mixed transition metal oxide material of claim 1 further characterized by an x-ray diffraction pattern comprising the peaks in Table A:
TABLE A
2θ (°)
d (Å)
100(I/I0)
34.5-36.5
2.460-2.598
vs
53-55
1.668-1.726
s to vs
55-58
1.589-1.668
w to m
58.5-62.5
1.485-1.576
vw
62.8-63.8
1.458-1.478
m.

### Claim 3 (depends on 1)

The mixed transition metal oxide material of claim 1 wherein the mixed transition metal oxide material is present in a mixture with at least one binder and wherein the mixture comprises up to 80 wt % binder.

### Claim 4 (depends on 3)

The mixed transition metal oxide material of claim 3 wherein the binder is selected from silicas, aluminas, silica-aluminas, titanias, zirconias, natural clays, synthetic clays, and mixtures thereof.

### Claim 5 (depends on 1)

The mixed transition metal oxide material of claim 1 wherein MI is Fe, Co, Ni, or any mixture thereof.

### Claim 6 (depends on 1)

The mixed transition metal oxide material of claim 1 wherein MII is Cr, Mo, or W.

### Claim 7 (depends on 1)

The mixed transition metal oxide material of claim 1 wherein MIII is Cr, Mo, or W and is different from MII.

### Claim 8 (depends on 1)

The mixed transition metal oxide material of claim 1 wherein the novel mixed transition metal oxide material is sulfided.

### Claim 9

A method of making a mixed transition metal oxide material having the formula:
(MIa)m(MIIb)n(MIIIc)oOeq
where:
MI is a metal or a mixture of metals selected from Group VIII (IUPAC Groups 8, 9, and 10);
MII is a metal selected from Group VI (IUPAC Group 6);
MIII is a metal selected from Group VI (IUPAC Group 6) which is different from MII;
a, b, c, and e are the valence state of MI, MII, MIII, and O;
m, n, o, and q are the mole ratio of MI, MII, MIII, and O, wherein m/(n+o) is from 1/10 to 10/1, wherein 0<n/o≤100 and 0≤o/n≤100, wherein q is greater than 0; and wherein a, b, c, e, m, n, o, and q satisfy the equation:
a*m+b*n+c*o+e*q=0
the material further characterized by an X-ray diffraction pattern comprising a broad peak between 2θ of 55° and 58° with the full width at half maximum larger than 3° and at least one of:
one or more sharp peaks between 2θ of 5° and 11.5° with the full width at half maximum less than 0.3°; and
one or more sharp peaks between 2θ of 11.5° and 32° with the full width at half maximum less than 0.6°;
the method comprising:
forming a reaction mixture containing a protic solvent, sources of MI, MII, and MIII, a basic solution, and at least one short-chain alkyl quaternary ammonium halide compound having the formula [R1 R2 R3 R4-N]X, where R1, R2, R3 and R4 are alkyl radicals having 1 to 6 carbon atoms, and R1, R2, R3 and R4 can be the same or different;
mixing the reaction mixture;
reacting the reaction mixture at a temperature from 25° C. to 200° C. for a period of time from 30 minutes to 200 hours to generate the mixed transition metal oxide material; and
recovering the mixed transition metal oxide material.

### Claim 10 (depends on 9)

The method of claim 9 wherein the recovering is by decantation, filtration or centrifugation.

### Claim 11 (depends on 10)

The method of claim 10 further comprising adding a binder to the reaction mixture or to the recovered mixed transition metal oxide material.

### Claim 12 (depends on 11)

The method of claim 11 wherein the binder is selected from aluminas, silicas, alumina-silicas, titanias, zirconias, natural clays, synthetic clays, and mixtures thereof.

### Claim 13 (depends on 9)

The method of claim 9 further comprising sulfiding at least a portion of the recovered mixed transition metal oxide material.

### Claim 14 (depends on 9)

The method of claim 9 further comprising adjusting the pH of the reaction mixture using an acidic or a basic solution.

### Claim 15 (depends on 9)

The method of claim 9 wherein the reacting is conducted under atmospheric pressure or autogenous pressure.

### Claim 16 (depends on 9)

The method of claim 9 wherein the forming the reaction mixture and the mixing are at the same time.

### Claim 17 (depends on 9)

The method of claim 9 further comprising mixing during the reacting.

### Claim 18 (depends on 9)

The method of claim 9 further comprising intermittent mixing during the reacting.

### Claim 19 (depends on 9)

The method of claim 9 wherein the temperature is varied during the reacting.

### Claim 20 (depends on 9)

The method of claim 9 wherein the material is further characterized by an x-ray diffraction pattern comprising the peaks in Table A:
TABLE A
2θ (°)
d (Å)
100(I/I0)
34.5-36.5
2.460-2.598
vs
53-55
1.668-1.726
s to vs
55-58
1.589-1.668
w to m
58.5-62.5
1.485-1.576
vw
62.8-63.8
1.458-1.478
m.

### Claim 21

A conversion process comprising contacting a material with a sulfiding agent to convert at least a portion of the material to at least one metal sulfide and contacting the metal sulfide with a feed at conversion conditions to generate at least one product, wherein the material comprises a mixed transition metal oxide material having the formula:
(MIa)m(MIIb)n(MIIIc)oOeq
where:
MI is a metal or a mixture of metals selected from Group VIII (IUPAC Groups 8, 9, and 10);
MII is a metal selected from Group VIB (IUPAC Group 6);
MIII is a metal selected from Group VIB (IUPAC Group 6) which is different from MII;
a, b, c, and e are the valence state of MI, MII, MIII, and O;
m, n, o, and q are the mole ratio of MI, MII, MIII, and O, wherein m/(n+o) is from 1/10 to 10/1, wherein 0<n/o≤100 and 0≤o/n≤100, wherein q is greater than 0; and wherein a, b, c, e, m, n, o, and q satisfy the equation:
a*m+b*n+c*o+e*q=0
the material further characterized by an X-ray diffraction pattern comprising a broad peak between 2θ of 55° and 58° with the full width at half maximum larger than 3° and at least one of:
one or more sharp peaks between 2θ of 5° and 11.5° with the full width at half maximum less than 0.3°; and
one or more sharp peaks between 2θ of 11.5° and 32° with the full width at half maximum less than 0.6°.

### Claim 22 (depends on 21)

The process of claim 21 wherein the conversion process is a hydrocarbon conversion process.

### Claim 23 (depends on 21)

The process of claim 21 wherein the conversion process is hydroprocessing.

### Claim 24 (depends on 21)

The process of claim 21 wherein the conversion process is selected from hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

### Claim 25 (depends on 21)

The process of claim 21 wherein the mixed transition metal oxide material is present in a mixture with at least one binder and wherein the mixture comprises up to 80 wt % binder.

### Claim 26 (depends on 21)

The process of claim 21 further characterized by an x-ray diffraction pattern comprising the peaks in Table A:
TABLE A
2θ (°)
d (Å)
100(I/I0)
34.5-36.5
2.460-2.598
vs
53-55
1.668-1.726
s to vs
55-58
1.589-1.668
w to m
58.5-62.5
1.485-1.576
vw
62.8-63.8
1.458-1.478
m.