# US 10,370,311 B2 · Hydrogen-assisted adsorption of sulphur compounds from olefin mixtures

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- Number: US 10,370,311 B2
- Document ID: US10370311B2
- Status: Granted
- Kind: B2
- Application number: 15/165,882
- Filed: 2016-05-26
- Published: 2016-12-01
- Granted: 2019-08-06
- Earliest claimed: 2015-05-28
- Assignees: Evonik Degussa GmbH
- Applicants: Evonik Degussa GmbH
- Inventors: Stephan Peitz; Guido Stochniol; Dietrich Maschmeyer; Helene Reeker; Reiner Bukohl
- Web page: https://patentgrep.com/patent/US10370311B2

## CPC

- C07C 7/12: by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- B01D 15/00: Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01J 20/06: comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J 20/08: comprising aluminium oxide or hydroxide; comprising bauxite
- C07C 2/06: of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C 2/56: Addition to acyclic hydrocarbons
- C07C 2/58: Catalytic processes
- C07C 5/327: Formation of non-aromatic carbon-to-carbon double bonds only
- C07C 5/48: with oxygen as an acceptor
- C07C 7/04: by distillation
- C07C 7/10: by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
- C07C 7/163: by hydrogenation
- C07C 7/167: for removal of compounds containing a triple carbon-to-carbon bond
- C07C 41/09: by dehydration of compounds containing hydroxy groups
- C07D 307/60: Two oxygen atoms, e.g. succinic anhydride
- C10G 25/003: {Specific sorbent material, not covered by C10G25/02 or C10G25/03}
- C10G 45/04: characterised by the catalyst used
- C10G 45/22: with hydrogen dissolved or suspended in the oil
- B01J 2220/42: Materials comprising a mixture of inorganic materials (materials coated or impregnated on a carrier B01J20/32)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- 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

The invention relates to a process for purifying hydrocarbon mixtures, in which a contaminated hydrocarbon mixture comprising olefins having three to eight carbon atoms is at least partly freed of sulphur-containing contaminants by contacting it with a solid sorbent, the hydrocarbon mixture being exclusively in the liquid state during the contact with the sorbent. The problem that it addressed was that of virtually completely removing sulphur compounds present in the mixture without forming new sulphur compounds again at the same time. At the same time, 1-butene present therein was not to be lost in the purification of the mixture. Finally, the sorbent used was to have a high sorption capacity, be very substantially free of carcinogenic constituents and be readily available. This problem is solved by using a sorbent based on copper oxide, zinc oxide and aluminium oxide in a particular composition, and by conducting the purification in the presence of a small amount of hydrogen.

## Claims

### Claim 1

A process for purifying hydrocarbon mixtures, in which a contaminated hydrocarbon mixture comprising olefins is at least partly freed of sulphur-containing contaminants by contacting the contaminated hydrocarbon mixture with a solid sorbent in the presence of hydrogen, wherein the contaminated hydrocarbon mixture, immediately prior to the contacting with the solid sorbent, contains hydrogen in a concentration, based on the total mass of the contaminated hydrocarbon mixture, between 1 ppm by weight and 10 000 ppm by weight, wherein the contaminated hydrocarbon mixture is exclusively in the liquid state during the contacting with the solid sorbent wherein the contaminated hydrocarbon mixture comprises 1-butene and the contacting with the solid sorbent converts less than 5% by weight of the 1-butene in the contaminated hydrocarbon mixture, wherein the solid sorbent has the following composition that adds up to 100% by weight:
copper oxide: 10% by weight to 60% by weight calculated as CuO;
zinc oxide: 10% by weight to 60% by weight calculated as ZnO;
aluminium oxide: 10% by weight to 30% by weight calculated as Al2O3; and
other substances: 0% by weight to 5% by weight,
wherein the solid sorbent has a copper oxide surface area of at least 50 m2/g,
and wherein the contaminated hydrocarbon mixture fulfills one of the following specifications A, B, C and D, each of which adds up to 100% by weight, the stated proportions by weight each being based on the total weight of the contaminated hydrocarbon mixture:
Specification A:
isobutane 15% to 45% by weight;
n-butane 5% to 18% by weight;
1-butene 5% to 20% by weight;
isobutene 12% to 25% by weight;
2-butenes 9% to 40% by weight;
1,3-butadiene 0% to 3% by weight;
water 0% to 1% by weight;
sulphur-containing impurities less than 0.5% by weight; and
hydrogen less than 1 ppm by weight;
Specification B:
isobutane 0.5% to 15% by weight;
n-butane 0.5% to 20% by weight;
1-butene 9% to 25% by weight;
isobutene 10% to 35% by weight;
2-butenes 3% to 15% by weight;
1,3-butadiene 25% to 70% by weight;
water 0% to 1% by weight;
sulphur-containing impurities less than 0.5% by weight; and
hydrogen less than 1 ppm by weight;
Specification C:
isobutane 0.5% to 18% by weight;
n-butane 0.5% to 25% by weight;
1-butene 9% to 40% by weight;
isobutene 10% to 55% by weight;
2-butenes 3% to 25% by weight;
1,3-butadiene 0% to 5% by weight;
water 0% to 1% by weight;
sulphur-containing impurities less than 0.5% by weight; and
hydrogen less than 1 ppm by weight; and
Specification D:
isobutane 0% to 20% by weight;
n-butane 10% to 35% by weight;
1-butene 0.2% to 45% by weight;
2-butenes 35% to 85% by weight;
water 0% to 1% by weight;
sulphur-containing impurities less than 0.5% by weight; and
hydrogen less than 1 ppm by weight.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the hydrogen is fully dissolved in the contaminated hydrocarbon mixture in the liquid state.

### Claim 3 (depends on 1)

The process according to claim 1, wherein the concentration of hydrogen is established by adding hydrogen to the contaminated hydrocarbon mixture immediately prior to the contacting with the solid sorbent, wherein the contaminated hydrocarbon mixture prior to addition of the hydrogen contains less than 1 ppm by weight of hydrogen.

### Claim 4 (depends on 1)

The process according to claim 1, wherein the solid sorbent has the following composition that adds up to 100% by weight:
copper oxide: 30% by weight to 45% by weight calculated as CuO;
zinc oxide: 30% by weight to 50% by weight calculated as ZnO;
aluminum oxide: 10% by weight to 15% by weight calculated as Al2O3;
further metal oxides: 0% by weight to 2% by weight;
graphite: 0% by weight to 3% by weight; and
other substances: 0% by weight to 1% by weight.

### Claim 5 (depends on 1)

The process according to claim 1, wherein the contacting with the solid sorbent is conducted under the following conditions:
a temperature range between 10° C. and 150° C.;
a pressure range between 0.5 and 3.5 MPa; and
a weight hourly space velocity range between 0.5 h−1 and 20 h−1.

### Claim 6 (depends on 1)

The process according to claim 1, wherein the contaminated hydrocarbon mixture contains, as sulphur-containing contaminant, at least one compound from one of the following substance classes:
a) thiols having the general formula R—SH where R is an alkyl, aryl, cycloalkyl or alkenyl radical;
b) disulphides having the general formula R—S—S—R′ where R and R′ are identical or different alkyl, aryl, cycloalkyl or alkenyl radicals;
c) sulphides having the general formula R—S—R′ where R and R′ are identical or different alkyl, aryl, cycloalkyl or alkenyl radicals; and
d) substituted or unsubstituted sulphur-containing heterocycles.

### Claim 7 (depends on 6)

The process according to claim 6, wherein the contaminated hydrocarbon mixture contains less than 0.2% by weight of the sulphur-containing contaminants, calculated as sulphur based on the total weight of the contaminated hydrocarbon mixture.

### Claim 8 (depends on 7)

The process according to claim 7, wherein the contaminated hydrocarbon mixture is freed by the contacting with the solid sorbent of at least 90% by weight of the sulphur-containing contaminants present in the contaminated hydrocarbon mixture.

### Claim 9 (depends on 7)

The process according to claim 7, wherein the contaminated hydrocarbon mixture is obtained from a pre-purification stage which pre-purifies a more highly contaminated raw material mixture to obtain the contaminated hydrocarbon mixture.

### Claim 10 (depends on 9)

The process according to claim 9, wherein the solid sorbent is used irreversibly.

### Claim 11 (depends on 1)

The process according to claim 1, wherein a hydrocarbon mixture which has been at least partly freed of contaminants by the process according to claim 1 is subjected to at least one of the workup steps enumerated below:
a) extraction of 1,3-butadiene present in the hydrocarbon mixture;
b) selective hydrogenation of diolefins and/or acetylenes present in the hydrocarbon mixture to olefins;
c) oligomerization of olefins present in the hydrocarbon mixture to corresponding oligomers;
d) distillative removal of 1-butene and/or isobutane present in the hydrocarbon mixture;
e) removal of isobutene present in the hydrocarbon mixture by conversion of the isobutene with water to tert-butanol and/or with methanol to methyl tert-butyl ether;
f) dehydrogenation of butanes present in the hydrocarbon mixture to butenes;
g) oxidative dehydrogenation of butenes present in the hydrocarbon mixture to butadiene;
h) alkylation of n-butene present in the hydrocarbon mixture with isobutane present therein; and
i) oxidation of hydrocarbons having four carbon atoms present in the hydrocarbon mixture for preparation of maleic anhydride.