# US 10,118,872 B2 · Phosphorous modified molecular sieves, their use in conversion of organics to olefins

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- Number: US 10,118,872 B2
- Document ID: US10118872B2
- Status: Granted
- Kind: B2
- Application number: 15/684,709
- Filed: 2017-08-23
- Published: 2018-03-29
- Granted: 2018-11-06
- Earliest claimed: 2007-07-31
- Assignees: Total Research & Technology Feluy
- Applicants: Total Research & Technology Feluy
- Inventors: Nikolai Nesterenko; Walter Vermeiren; Delphine Minoux; Sander Van Donk
- Web page: https://patentgrep.com/patent/US10118872B2

## CPC

- C07C 1/322: {the hetero-atom being a sulfur atom}
- B01J 29/40: of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J 29/85: Silicoaluminophosphates [SAPO compounds]
- C01B 39/026: {After-treatment}
- C07C 1/20: starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C 1/22: by reduction
- C07C 1/26: starting from organic compounds containing only halogen atoms as hetero-atoms
- C07C 2/06: of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C 4/06: Catalytic processes {(C07C4/025 takes precedence)}
- C07C 7/04: by distillation
- C10G 3/00: Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids (production from non-melting solid oxygen-containing carbonaceous materials C10G1/00)
- B01J 2229/36: Steaming
- B01J 2229/37: Acid treatment
- C07C 2529/85: Silicoaluminophosphates (SAPO compounds)
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2300/4081: Recycling aspects
- C10G 2400/20: C2-C4 olefins
- Y02P 20/52: using catalysts, e.g. selective catalysts
- Y02P 30/20: using bio-feedstock
- Y02P 30/40: Ethylene production
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention is a phosphorous modified zeolite (A) made by a process comprising in that order: selecting a zeolite with low Si/Al ratio (advantageously lower than 30) among H+ or NH4+-form of MFI, MEL, FER, MOR, clinoptilolite, said zeolite having been made preferably without direct addition of organic template; steaming at a temperature ranging from 400 to 870° C. for 0.01-200h; leaching with an aqueous acid solution containing the source of P at conditions effective to remove a substantial part of Al from the zeolite and to introduce at least 0.3 wt % of P; separation of the solid from the liquid; an optional washing step or an optional drying step or an optional drying step followed by a washing step; a calcination step. The present invention also relates to a process (hereunder referred as “XTO process”) for making an olefin product from an oxygen-containing, halogenide-containing or sulphur-containing organic feedstock wherein said oxygen-containing, halogenide-containing or sulphur-containing organic feedstock is contacted with the above catalyst (in the XTO reactor) under conditions effective to convert at least a portion of the oxygen-containing, halogenide-containing or sulphur-containing organic feedstock to olefin products (the XTO reactor effluent). The present invention also relates to a process (hereunder referred as “combined XTO and OCP process”) to make light olefins from an oxygen-containing, halogenide-containing or sulphur-containing organic feedstock comprising: contacting said oxygen-containing, halogenide-containing or sulphur-containing organic feedstock in the XTO reactor with the above catalyst at conditions effective to convert at least a portion of the feedstock to form an XTO reactor effluent comprising light olefins and a heavy hydrocarbon fraction; separating said light olefins from said heavy hydrocarbon fraction; contacting said heavy hydrocarbon fraction in the OCP reactor at conditions effective to convert at least a portion of said heavy hydrocarbon fraction to light olefins.

## Claims

### Claim 1

A process comprising:
contacting an halogenide-containing feedstock in a first reactor with a catalyst under conditions effective to convert the halogenide-containing feedstock to a first reactor effluent comprising olefin products, wherein the catalyst comprises a phosphorus modified zeolite having a P content ranging between 0.3 and 7 weight percent, wherein the phosphorus modified zeolite is made by a process comprising:
selecting a zeolite having a Si:Al atomic ratio of 30 or less, wherein the zeolite is selected from the group consisting of MFI, MEL, FER, MOR, and clinoptilolite, and wherein the selected zeolite is in the H+ or NH4+ form;
steaming the zeolite at a temperature ranging from 400° C. to 870° C. for 0.01 h to 200 h;
leaching the zeolite with an aqueous acid solution containing a source of P at conditions effective to remove a substantial amount of Al from the zeolite and to introduce more than 0.3 wt % of P, wherein the aqueous acid solution containing the source of P comprises a salt of a phosphate ([PO4]3−), an acid or a corresponding salt of a phosphite ([HPO3]2−), an acid or a corresponding salt of a hypophosphite ([H2PO2]1−), an acid or a corresponding salt of a diphosphate, or an acid or a corresponding salt of a polyphosphate;
separating the zeolite from the aqueous acid solution; and
calcining the zeolite;
wherein the first reactor effluent comprises light olefins and a heavy hydrocarbon fraction and is sent to a first fractionator to separate the light olefins from the heavy hydrocarbon fraction, and wherein the heavy hydrocarbon fraction is sent to a second reactor at conditions effective to convert at least a portion of the heavy hydrocarbon fraction to light olefins, wherein a catalyst in the second reactor is the same as the catalyst in the first reactor.

### Claim 2 (depends on 1)

The process of claim 1, wherein the first reactor effluent comprises light olefins and a heavy hydrocarbon fraction and is sent to a first fractionator to separate the light olefins from the heavy hydrocarbon fraction, and wherein the heavy hydrocarbon fraction is recycled to the first reactor at conditions effective to convert at least a portion of the heavy hydrocarbon fraction to olefin products.

### Claim 3 (depends on 1)

The process of claim 1, wherein the olefin products include ethylene and propylene that are fractionated to form a stream comprising ethylene, and wherein at least a part of the stream comprising ethylene is recycled to the first reactor to increase propylene production.

### Claim 4 (depends on 1)

The process of claim 1, wherein a second reactor effluent is sent to a second fractionator and the light olefins are recovered, and wherein heavy hydrocarbons having 4 or more carbon atoms are recycled to the second reactor and mixed with the heavy hydrocarbons recovered from the first reactor effluent.

### Claim 5 (depends on 4)

The process of claim 4, wherein the heavy hydrocarbons having 4 or more carbon atoms are sent to a third fractionator to remove a heavy hydrocarbon stream comprising C6+ hydrocarbons prior to recycling to the second reactor.

### Claim 6 (depends on 4)

The process of claim 4, wherein the olefin products include ethylene and propylene, wherein ethylene is recycled to the second reactor to adjust a propylene to ethylene production ratio, and wherein the ethylene is recycled from the first fractionator, the second fractionator, both the first fractionator and the second fractionator, or a common recovery section.

### Claim 7 (depends on 4)

The process of claim 4, wherein the olefin products include ethylene and propylene, wherein ethylene is recycled to the first reactor to adjust a propylene to ethylene production, and wherein the ethylene is recycled from the first fractionator, the second fractionator, both the first fractionator and the second fractionator, or from a common recovery section.

### Claim 8 (depends on 1)

The process of claim 1, wherein the olefin products include ethylene, and wherein the ethylene is polymerized with one or more comonomers.

### Claim 9 (depends on 1)

The process of claim 1, wherein the olefin products include propylene, and wherein the propylene is polymerized with one or more comonomers.

### Claim 10 (depends on 9)

The process of claim 9, wherein a ratio of ethylene to the oxygen-containing feedstock fed to the first reactor is 1.8 or less.

### Claim 11 (depends on 1)

The process of claim 1, wherein the first reactor is operated at a temperature ranging from about 200° C. to 700° C., and wherein a partial pressure of the oxygen-containing feedstock ranges from about 5 kPa to about 5 MPa.

### Claim 12 (depends on 1)

The process of claim 1, wherein the halogenide-containing feedstock is contacted in the first reactor with the catalyst in the presence of an inert diluent, wherein the inert diluent is present in an amount ranging from 1 to 95 molar percent based on a total number of moles of the inert diluent and the halogenide-containing feedstock.

### Claim 13 (depends on 1)

The process of claim 1, wherein greater than 50 weight % of olefins having 4 carbon atoms or more in the first reactor effluent are butenes.

### Claim 14 (depends on 1)

The process of claim 1, wherein more than 80% by weight of hydrocarbons having 4 carbon atoms or more in the first reactor effluent are C4 to C8 olefins.

### Claim 15 (depends on 1)

The process of claim 1, wherein the aqueous acid solution containing the source of P comprises phosphorous acid (H3PO3).

### Claim 16 (depends on 1)

The process of claim 1, wherein the phosphorus modified zeolite comprises ZSM-5.