# US 9,751,816 B2 · Method for producing light unsaturated hydrocarbons

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- Number: US 9,751,816 B2
- Document ID: US9751816B2
- Status: Granted
- Kind: B2
- Application number: 15/105,398
- Filed: 2013-12-17
- Published: 2016-11-03
- Granted: 2017-09-05
- Earliest claimed: 2013-12-17
- Assignees: Braskem S.A.
- Applicants: Braskem S.A.
- Inventors: Maria Ignez Broglio; Augusto Teruo Morita; Roberto Werneck do Carmo; Luis Felipe de Souza Tavares; Bruno Maia Moreira
- Web page: https://patentgrep.com/patent/US9751816B2

## CPC

- C07C 1/24: by elimination of water
- C07C 1/20: starting from organic compounds containing only oxygen atoms as heteroatoms
- C10G 3/40: {Thermal non-catalytic treatment}
- C10G 9/00: Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C07C 2529/40: of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C 2529/85: Silicoaluminophosphates (SAPO compounds)
- C10G 2400/20: C2-C4 olefins
- C10G 2400/22: Higher olefins
- Y02P 30/20: using bio-feedstock
- C07C: ACYCLIC OR CARBOCYCLIC 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention relates to a process of producing partly renewable light unsaturated hydrocarbons, in which at least one pyrolysis furnace of a unit for producing light unsaturated hydrocarbons from hydrocarbons is replaced by at least one reactor for conversion of ethanol to light unsaturated hydrocarbons.

## Claims

### Claim 1

A process for producing partly renewable light unsaturated hydrocarbons, comprising:
(a) contacting ethanol with an acid catalyst in at least one reactor under conditions suitable to form a reaction effluent stream comprising water, ethene, propene and unsaturated hydrocarbons with four carbon atoms, besides other co-products of secondary reactions;
(b) feeding the stream generated in (a) to a direct-contact cooling unit under conditions suitable to form a top stream containing most of the light unsaturated hydrocarbons present in the effluent stream of step (a) and a bottom stream containing most of the water present in the effluent stream of step (a);
(c) compressing the top stream rich in light unsaturated hydrocarbons generated in (b);
(d) contacting naphtha with steam in a pyrolysis furnace of an existing cracking unit under conditions suitable to form a cracking effluent stream comprising light unsaturated hydrocarbons, fuel oil, gas oil and gasoline;
(e) separating the effluent generated in the cracking reaction (d) into a light hydrocarbon stream containing most of the light unsaturated hydrocarbons present in the effluent of step (d) and at least one heavy hydrocarbon stream;
(f) feeding the stream rich in light unsaturated hydrocarbons from step (e) to a direct-contact cooling unit under conditions suitable to form a top stream containing most of the light unsaturated hydrocarbons present in the effluent of reaction (e) and a bottom stream containing the condensed compounds and most of the water present in the effluent of reaction (d);
(g) compressing the top stream rich in unsaturated hydrocarbons generated in (f);
(h) combining the streams (c) and (g) and conducting them to the steps of separating and purifying unsaturated hydrocarbons C2, C3 and C4 of the existing cracking unit, wherein said pyrolysis furnace of said existing cracking unit is gradually replaced by reactors for conversion of ethanol to light unsaturated hydrocarbons.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the top stream generated in (b) is contacted with a base solution in a caustic wash unit under conditions suitable to remove at least part of the CO2 from the stream before it is compressed in step (c).

### Claim 3 (depends on 2)

The process according to claim 2, wherein the top stream generated in (f) is contacted with a base solution in a caustic wash unit under conditions suitable to remove at least part of the CO2 from the stream before it is compressed ion step (g).

### Claim 4 (depends on 1)

The process according to claim 1, wherein the stream combined in (h) is contacted with a base solution in a caustic wash unit under conditions suitable to remove at least part of the CO2 from the stream before it is sent to the steps of separating and purifying unsaturated hydrocarbons C2, C3 and C4 of the existing cracking unit.

### Claim 5 (depends on 1)

The process according to claim 1, characterized in that the stream of hydrocarbons of fossil origin used as raw material in the production of light unsaturated hydrocarbons comprises hydrocarbons in the range from C2 to C40.

### Claim 6 (depends on 5)

The process according to claim 5, wherein the stream of hydrocarbons of fossil origin used as raw material in the production of light unsaturated hydrocarbons comprises hydrocarbons ranging from C2 to C30.

### Claim 7 (depends on 6)

The process according to claim 6, wherein the stream of hydrocarbons of fossil origin used as raw material in the production of light unsaturated hydrocarbons comprises hydrocarbons ranging from C2 to C20.

### Claim 8 (depends on 7)

The process according to claim 7, wherein the stream of hydrocarbons of fossil origin used as raw material in the production of light unsaturated hydrocarbons comprise hydrocarbons ranging from C5 to C12 with boiling point of naphtha ranging from about 36° C. to about 195° C.

### Claim 9 (depends on 1)

The process according to claim 1, wherein the ethanol used as raw material for the process of converting ethanol to light unsaturated hydrocarbons is obtained by fermenting at least one organic substrate from renewable natural raw materials.

### Claim 10 (depends on 9)

The process according to claim 9, wherein the ethanol used as raw material for the process of converting ethanol to light unsaturated hydrocarbons is either hydrated or anhydrous ethanol.

### Claim 11 (depends on 10)

The process according to claim 10, wherein the ethanol used as raw material for the process of converting ethanol to light unsaturated hydrocarbons is fuel-grade hydrated ethanol.

### Claim 12 (depends on 1)

The process according to claim 1, wherein the reaction products from the conversion of ethanol to unsaturated hydrocarbons exhibit, in their composition (on dry base), from 15 to 60% by mole of ethene, from 5 to 40% by mole of propene and from 3 to 35% by mole of C4, C4 being a mixture of 1 and 2-butenes.

### Claim 13 (depends on 12)

The process according to claim 12, wherein the composition of C4 comprises a mixture of 1 and 2-butenes and 1,3-butadiene.

### Claim 14

A process for producing partly renewable light unsaturated hydrocarbons, comprising:
(a) contacting ethanol with an acid catalyst in at least one reactor under conditions suitable to form a reaction effluent stream comprising water, ethene, propene and unsaturated hydrocarbons with four carbon atoms, besides other co-products of secondary reactions;
(b) feeding the stream generated in (a) to a direct-contact cooling unit under conditions suitable to form a top stream containing most of the light unsaturated hydrocarbons present in the effluent stream of step (a) and a bottom stream containing most of the water present in the effluent stream of step (a);
(c) contacting naphtha with steam in a pyrolysis furnace of an existing cracking unit under conditions suitable to from a cracking effluent stream comprising light unsaturated hydrocarbons, fuel oil, gas oil and gasoline;
(d) separating the effluent generated in the cracking reaction (c) into a light unsaturated hydrocarbon stream containing most of the light unsaturated hydrocarbons present in the effluent of step (c) and at least one heavy hydrocarbon stream;
(e) feeding the stream rich in light unsaturated hydrocarbons from step (d) to a direct-contact cooling unit under conditions suitable to form a top stream containing most of the light unsaturated hydrocarbons present in the effluent of reaction (d) and a bottom stream containing the condensed compounds and most of the water present in the effluent of reaction (c);
(f) combining the streams (b) and (e) and contacting them with a base solution in a caustic wash unit under conditions suitable to remove at least a part of the CO2 from the stream and sending them to the steps of separating and purifying unsaturated hydrocarbons C2, C3 and C4 of the existing cracking unit, wherein said pyrolysis furnace of said existing cracking unit is gradually replaced by reactors for conversion of ethanol to light unsaturated hydrocarbons.

### Claim 15

A process for producing partly renewable light unsaturated hydrocarbons, comprising:
(a) contacting ethanol with an acid catalyst in at least one reactor under conditions suitable to form a reaction effluent stream comprising water, ethene, propene and unsaturated hydrocarbons with four carbon atoms, besides other co-products of secondary reactions;
(b) contacting naphtha with steam in a pyrolysis furnace of an existing cracking unit under conditions suitable to form a cracking effluent stream comprising light unsaturated hydrocarbons, fuel oil, gasoil and gasoline;
(c) separating the effluent generated in the cracking reaction (c) into a light unsaturated hydrocarbon stream containing most of the light unsaturated hydrocarbons present ion the effluent of step (c) and at least one heavy hydrocarbon stream;
(d) combining the effluent stream of the step of converting ethanol to unsaturated hydrocarbons (a) and the light unsaturated hydrocarbon stream generated in step (c) before the direct-contact fooling step for removal of condensates and water, followed by contact with a base solution in a caustic wash unit under conditions suitable to remove at least a part of the CO2 from the stream and from the steps of separating and purifying unsaturated hydrocarbons C2, C3 and C4 of the existing cracking unit, wherein said pyrolysis furnace of said existing cracking unit is gradually replaced by reactors for conversion of ethanol to light unsaturated hydrocarbons.