NL2007874C2

NL2007874C2 - The application of chemical compounds presents a styrene production process in a fuel.

Info

Publication number: NL2007874C2
Application number: NL2007874A
Authority: NL
Inventors: Michael Dirk Boot; Henricus Antoine Maria Water
Original assignee: Progression Industry B V
Priority date: 2011-11-25
Filing date: 2011-11-25
Publication date: 2013-05-28
Also published as: WO2013077738A1

Abstract

The present invention relates to a method for the preparation of a fuel, by the addition of one or more components to a base fuel, wherein the method comprises the following steps: . i) providing a base fuel, . ii) withdrawing aromatic components from a styrene / propylene ox ide production plant, . iii) adding the components obtained according to step ii) to said base fuel obtained according to step i) for the preparation of said fuel. The invention further relates to a fuel obtainable by the method.

Description

Title: The application of chemical compounds presents a styrene production process in a fuel.

The present invention relates to the use of chemical compounds present a styrene 5 production process in a commercial fuel.

Cyclic oxygenates, like 1-phenylethanol, 2-phenylethanol, acetophenon, benzaldehyde, benzyl alcohol and dimers of these products, are present in large quantities in the chemical process that produces two products, propylene oxide and styrene monomer. Companies like Shell Chemicals, Repsol and Lyondell Basell, are 10 operating these types of processes in various parts of the world. Not all processes are exactly the same, but the earlier mentioned products are in all these processes present. Commercially styrene is also co-produced with propylene oxide in a process known as POSM (Lyondell Chemical Company) or SM/PO (Shell) for styrene monomer / propylene oxide. In this process ethyl benzene is treated with oxygen to form the ethyl benzene 15 hydro peroxide. This hydro peroxide is then used to oxidize propylene to propylene oxide. The resulting 2-phenylethanol is dehydrated to give styrene.

International application WO 2005/054157 relates to a method for manufacturing styrene, i.e. the coproduction of propylene oxide and styrene starting from ethyl benzene. Such a process involves the steps of (i) reacting ethyl benzene with oxygen or air to form 20 ethyl benzene hydro peroxide, (ii) reacting the ethyl benzene hydro peroxide thus obtained with propene in the presence of an epoxidation catalyst to yield propylene oxide and 1-phenyl-ethanol, and (iii) converting the 1-phenyl-ethanol into styrene by dehydration using a suitable dehydration catalyst.

US Patent No 6504038 relates to a process for the joint preparation of styrene 25 and propylene oxide. Such process is commonly referred to as styrene monomer/propylene oxide (SM/PO) process. In general, a SM/PO process comprises the steps of: (a) reacting ethene and benzene to form ethyl benzene, (b) reacting ethyl benzene with oxygen or air to form ethyl benzene hydro peroxide, (c) reacting at least part of the ethyl benzene hydro peroxide obtained with propene in the presence of an 30 epoxidation catalyst to form propylene oxide and 1-phenyl ethanol, and (d) dehydrating at least part of the 1-phenyl ethanol obtained into styrene in the presence of a suitable dehydration catalyst.

The above SM/PO process is well known in the art. In step (a) ethyl benzene is formed by the alkylation of benzene in an ethyl benzene unit. The benzene can, for 35 instance, be derived from a platformer, whilst ethene can be derived from a steam 2 cracking unit. A further suitable process is the process known as the Mobil/Badger process. In this process a synthetic zeolite catalyst, ZSM-5, is used. The preparation of ethyl benzene from ethene and benzene over a zeolitic catalyst is disclosed in U.S.Pat.No. 4,107,224. Step (a) of the process can be carried out independently from 5 process steps (b) to (d), i.e. at a different location. However, it is preferred that the ethyl benzene production matches the styrene production in step (d), so that the ethyl benzene unit is an integrated part of the SM/PO process or is located in the vicinity of a SM/PO plant. A SM/PO plant with an integrated ethyl benzene unit is generally preferred.

In the oxidation step (b) liquid phase oxidation of ethyl benzene into ethyl benzene 10 hydro peroxide occurs at a temperature of 100-160[deg.] C and at a pressure of 1-4 bar. The oxidation is typically carried out with air as the oxidizing gas, but oxygen may also be applied. The main by-product formed at this stage is acetophenone, which may be hydrogenated in the SM/PO process into 1-phenylethanol, used in step (d) to produce styrene. In the epoxidation step (c) ethyl benzene hydro peroxide is reacted with propene 15 to yield propylene oxide and 1-phenyl ethanol or substituted 1-phenyl ethanol. In such epoxidation step a homogeneous catalyst or a heterogeneous catalyst can be applied. The effluent from the epoxidation step is normally first subjected to a separation treatment to remove the propylene oxide formed, after which the residual stream, containing 1-phenyl ethanol, is suitably subjected to one or more further separation treatments, inter 20 alia to remove ethyl benzene for reuse in an earlier stage of the process. The eventually obtained 1-phenyl ethanol containing stream is then subjected to the dehydration treatment in step (d). The dehydration of 1-phenyl ethanol into styrene can be carried out both in the gas phase and in the liquid phase. Dehydration conditions include reaction temperatures of 100-210[deg.] C. for liquid phase dehydration and 210-320[deg.j C., 25 typically 280-310[deg.] C., for gas phase dehydration. Pressures usually range from 0.1 to 10 bar. In principle any known dehydration process can be applied in step (d).

In a commercial SM/PO process the propene used in step (c) can be supplied either from an external source or can be made at the SM/PO site itself, normally in a steam cracking unit (also commonly referred to as ethene plant). A SM/PO process 30 comprising the steps (a) to (d) as described above requires equal amounts of ethene and propene as feedstock. Because of this, SM/PO plants are typically located in the vicinity of an ethene plant, which produces both the required ethene and propene. Accordingly, if a new SM/PO plant is to be designed and built, this plant is normally either located near an existing ethene plant having an overcapacity of ethene and propene or an ethene plant 35 must be included in the design to ensure the necessary ethene and propene.

3

Products like 1-phenylethanol and acetophenon are so called styrene precursors. These are intermediates that are formed in this PO-SM or SM-PO process. Products like benzaldehyde, benzylalcohol and to some extent 2-phenylethanol and the dimers will not be converted into styrene monomer. Consequently they have a lower value more close to 5 fuel value or even lower.

In the PO-SM and SM-PO process, the streams that contain these chemical compounds, are stored in large storage tanks and the non styrene precursors are extracted from the process via various distillation steps. Consequently all the above mentioned chemical products can be taken out of the process or production unit in a 10 simple way.

An object of the present invention is to use of the aromatic, oxygen rich components present in the styrene process for another application.

Another object of the present invention is to manufacture a fuel having a high caloric value.

15 The present invention thus relates to a method for the preparation of a fuel, by the addition of one or more additives to a base fuel, wherein the method comprises the following steps: i) providing a base fuel, ii) withdrawing aromatic components from a styrene production plant, 20 iii) adding the components obtained according to step ii) to said base fuel obtained according to step i) for the preparation of said fuel.

In a preferred embodiment of the present invention the aromatic components in step ii) comprise oxygenated aromatic components. The base fuel according to step i) is selected from the group consisting of diesel fuel, jet fuel, kerosine, gasoline, bunker fuel, 25 synthetic or Fischer-Tropsch fuels, vegetable oils and so-termed biofuels, and mixtures thereof, especially selected from the group of jet fuel, gasoline and diesel.

In an embodiment the styrene production plant according to step i) is a process selected from the group PO-SM process and SM-PO process.

The aromatic components in step ii) comprise preferably styrene precursor 30 components, and the aromatic components in step ii) comprise preferably waste products that have not been converted into styrene monomer. Examples of styrene precursor components in step ii) comprise one or more of 1-phenylethanol, 2-phenylethanol and acetophenon. Examples of the waste products comprise one or more of benzaldehyd, benzyl alcohol, BPE and dimers like DPEE (diphenylene ethyl ether).

35 4

The present invention relates furthermore to a fuel, comprising a base fuel and one or more additives, wherein one or more additives are aromatic components and originate from a styrene production plant. The base fuel is preferably selected from the group consisting of diesel fuel, jet fuel, kerosine, gasoline, bunker fuel, synthetic or 5 Fischer-Tropsch fuels, vegetable oils and so-termed biofuels, and mixtures thereof.

In an embodiment the styrene production plant is a process selected from the group PO-SM process and SM-PO process.

The present fuel is characterized in that said one or more additives are chosen from the group consisting of 1-phenylethanol, 2-phenylethanol, acetophenon, 10 benzaldehyd, benzyl alcohol, BPE and dimers like DPEE (diphenylene ethyl ether), or mixtures thereof.

The present inventors found that jet fuel without aromatic hydrocarbons the seals in the fuel circuit will shrink during flight and cause: Synthetic Fischer-Tropsch kerosene is blended because, unlike conventional jet fuel, it contains no aromatic hydrocarbons. While 15 partially responsible for the smoke and soot produced by gas turbines, aromatics also cause elastomeric engine seals to swell.

In addition, for gasoline, the aromatic base generally increases the octane number of the gasoline base fuel. And for diesel, the cyclic oxygenates reduce soot emissions in diesel engines when blended to diesel fuel.

20 Products like 1-phenylethanol, benzylalcohol and 2-phenylethanol are polar in nature. Accordingly, dissolving such compounds in diesel fuel might require additional surfactant additives and/or elevated fuel temperatures to keep the phases together. In a preferred embodiment the whole stream (i.e. polar + non-polar fractions) is added to diesel first. Subsequently, the polar phase (which does not dissolve and has diesel 25 floating on top) can be extracted and added to either kerosene (jet fuel), gasoline or both. According to another embodiment the whole stream is added directly to gasoline, kerosene (jet fuel) or both.

The liquid fuel composition according to the present invention may contain one or more of the usual additives, such as agents affecting flow at low temperatures, agents 30 suppressing the precipitation of waxy components, stabilisers, antioxidants, agents for improving the cetane number, agents for promoting combustion, detergents, defoaming agents, lubricants, antifoaming agents, antistatic agents, agents for promoting conductivity, corrosion-suppressing agents, fragrances, pigments, friction-reducing agents and the like. The additives commonly used to reduce the emission of nitrogen oxides may 35 also be used in the present liquid fuel.

5

The present invention relates to the application of specific process streams as additive in a fuel, either in neat form or blended to other fuels, in combustion engines (e.g. compression-ignition, spark-ignition, jet turbines) or burners (e.g. domestic for heating), as swell enhancing compound in jet fuel,.as octane booster in gasoline fuel, as soot reducing 5 compound in diesel fuel.

The present invention will now be illustrated by way of an example. This example is for illustrative purposes only and does not limit the scope of the present invention.

BRIEF DESCRIPTION OF FIGURE.

10 The sole Figure shows the general concept underlying the present invention. The PO-SM process and SM-PO process is depicted with reference B. Process B has basically two output streams C and D. Stream C is the styrene product, whereas D are the waste products or the products not converted into styrene. Examples of D are benzaldehyd, benzyl alcohol, BPE and dimers like DPEE (diphenylene ethyl ether).

15 Please note that this list is not limitative. The styrene precursors are indicated with reference A. Examples of A are 1-phenylethanol and acetophenone.

The invention must be seen in the extraction of (parts of) A and D into F, wherein F refers to a base fuel. This means that according the Figure a fuel is prepared by the addition of valuable components from a styrene production plant B, i.e. streams indicated 20 at D and A, to a base fuel.

Claims

Method for the preparation of a fuel, by adding one or more additives to a basic fuel, characterized in that the method comprises the following steps: i) providing a basic fuel ii) extracting aromatic constituents from a styrene factory iii) adding the components obtained in step ii) to the base fuel obtained in step i) to prepare the fuel.

Method according to claim 1, characterized in that the aromatic components in step ii) comprise oxygen-containing aromatic components.

Method according to one or more of the preceding claims, characterized in that the base fuel according to step i) is selected from the group consisting of diesel fuel, aircraft fuel, kerosene, gasoline, bunker fuel, synthetic or Fischer-Tropsch fuels, vegetable oils and so-called biofuels, and mixtures thereof.

A method according to claim 3, characterized in that the base fuel is selected from the group of jet fuel, gasoline and diesel.

Method according to one or more of the preceding claims, characterized in that the styrene factory according to step i) is a process selected from the group PO-SM process and SM-PO process.

6. Method according to one or more of the preceding claims, characterized in that the aromatic components in step ii) comprise styrene precursor components.

Process according to one or more of the preceding claims, characterized in that the aromatic constituents in step ii) comprise residual products that have not been converted into styrene monomer.

8. Process according to claim 6, characterized in that the styrene precursor components in step ii) comprise one or more of 1-phenylethanol, 2-phenylethanol and acetophenone.

A method according to claim 7, characterized in that the residual products comprise one or more of benzaldehyde, benzyl alcohol, BPE and dimers such as DPEE (diphenylene ethyl ether). 20 078 74

A fuel comprising a basic fuel and one or more additives, characterized in that the one or more additives are aromatic components and come from a styrene factory.

11. Fuel according to claim 10, characterized in that the basic fuel is selected from the group consisting of diesel fuel, jet fuel, kerosene, gasoline, bunker fuel, synthetic or Fischer-Tropsch fuels, vegetable oils and so-called biofuels, and mixtures thereof.

12. Fuel according to one or more of claims 10-11, characterized in that the styrene plant is a process selected from the group PO-SM process and SM-PO process.

13. Fuel according to one or more of claims 10-12, characterized in that one or more additives are selected from the group consisting of 1-phenylethanol, 2-phenylethanol and acetophenone, benzaldehyde, benzyl alcohol, BPE and dimers such as DPEE (diphenylene ethyl ether), or mixtures thereof. 20 07 8 74