WO2015013350A1

WO2015013350A1 - PROCESS FOR PREPARING C10 to C30 ALCOHOLS

Info

Publication number: WO2015013350A1
Application number: PCT/US2014/047719
Authority: WO
Inventors: Jr. David Morris Hamilton; Anand Nilekar; Nicoleta Cristina NENU; Smita EDULJI; Nitish NAIR
Original assignee: Shell Oil Company; Shell Internationale Research Maatschappij B.V.
Priority date: 2013-07-25
Filing date: 2014-07-23
Publication date: 2015-01-29

Abstract

The present invention provides a process for preparing C10 to C30 alcohols, comprising the following steps: (i) reacting aliphatic, non-cyclic C10 to C30 olefins with N₂O to obtain an oxidation reaction product comprising C10 to C30 carbonyls; (ii) reducing at least part of the C10 to C30 carbonyls in the oxidation reaction product to the corresponding C10 to C30 alcohols, wherein the aliphatic, non-cyclic C10 to C30 olefins are reacted with the N₂O in step (i) by: (i-a) providing a liquid olefin feed comprising aliphatic, non-cyclic C10 to C30 olefins; (i-b) providing an oxidant feed comprising at least 5% by volume of N₂O, based on the total oxidant feed; and (i-c) contacting the liquid olefin feed and the oxidant feed with a porous material in a reactor at a temperature in the range of from 150 to 500º C and a pressure in the range of from 10 to 300 bar. In another aspect the invention provides a process or producing surfactant compounds and a method of treating a crude oil containing formation.

Description

PROCESS FOR PREPARING CIO to C30 ALCOHOLS

The present application claims the benefit of pending U.S. Provisional Patent Application Serial No.

61/858277, filed July 25, 2013.

Field of the Invention

The present invention relates to a process for preparing CIO to C30 alcohols and a process for preparing surfactants compounds. In another aspect the invention provides a method of treating a crude oil containing formation .

Background of the Invention

A large variety of products useful, for instance, as nonionic surfactants, wetting and emulsifying agents, solvents and chemical intermediates are prepared by the addition reaction (alkoxylation reaction) of alkylene oxides (epoxides) with organic compounds having one or more active hydrogen atoms . For example, particular mention may be made of the alcohol ethoxylates prepared by the reaction of ethylene oxide with aliphatic, non- cyclic alcohols of 10 to 30 carbon atoms. Such

ethoxylates, and to a lesser extent corresponding propoxylates and compounds containing mixed oxyethylene and oxypropylene groups, are widely employed as nonionic detergent components in cleaning and personal care formulations .

Sulfonated alcohol alkoxylates have a wide variety of uses as well, especially as anionic surfactants.

Sulfonated higher secondary alcohol ethoxylates (SAES) offer comparable to better properties in bulk

applications relative to anionics like linear alkyl benzene sulfonates and primary alcohol ethoxy sulfates, as well as methyl ester sulfonates. These materials may l be used to produce household detergents including laundry powders, laundry liquids, dishwashing liquids and other household cleaners, as well as lubricants and personal care compositions.

The secondary alcohol ethoxylates and its sulfonated products are significantly more environmentally benign compared to the linear alkyl benzene based surfactants and have better pour point and surface tension reduction behaviour compared to primary alcohol ethoxylates and derived surfactants.

Another application of the above described alcohols is in chemically enhanced oil recovery. In particular secondary alcohol ethoxylates and/or propoxylates and their sulfonated products are used in chemically enhanced oil recovery.

Primary alkoxylated alcohols may for instance be made by an ethylene oligomerization process to give primary olefin and hydroformylating the primary olefins into an oxo-alcohol. Alkoxylation of the resulting alcohol by reaction with a suitable alkylene oxide such as ethylene oxide or propylene oxide will give the primary

alkoxylated alcohols. The above described process for preparing is less suitable for preparing secondary alcohol alkoxylates, due to the difficulty to

hydroformulate secondary olefins. Alternatively,

secondary alcohols may be made directly from paraffins. A well know method for preparing secondary alcohols from paraffins is by oxidation of the paraffins using boric acid as a catalyst. Such a process is for instance described in WO2009058654. Although the boron reagents used herein are referred to as catalyst, strictly speaking, they are not a catalyst as they are consumed in the reaction. Its function is to protect the oxygenate (sec-alcohol) by reaction to give an oxidation-resistant borate ester. Oxidation of paraffins with oxygen using boric acid as for instance described in WO2009058654 is a complex process including many separate process steps. The steps include at least (1) mixing part of the paraffin and boric acid, (2) dehydrating the mixture to form metaboric acid, (3) adding remaining paraffin, (4) adding oxidant to form secondary alcohol borate esters, (5) separating unreacted paraffins and by-products, (6) hydrolyzing, methanolyzing or alcoholyzing the borate esters to form secondary alcohols and boric acid or borates, (7) separation of the secondary alcohol from boric acid and subsequently (8) recovering the alcohols.

One disadvantage of this process is the need to replenish the boric acid catalyst. According to

US3796761, the boric acid recovery and recycle is challenging and make the process economically

unattractive. Boric acid cannot just be recycled but would need to be dehydrated prior to being used again. In addition to the need to replenish the boric acid

catalyst, another distinct disadvantage is that most of these steps are carried out using different reaction conditions requiring several reheating, and optionally cooling cycles.

IN2002DE01134 discloses a process for preparing secondary alcohols by liquid phase oxidation. The invention is particularly concerned with a catalytic process for preparing of secondary alcohols by oxidation of n-alkanes with molecular oxygen in presence of boric acid solution. According to IN2002DE01134 , boric acid oxidations result in poor activity and low yields because of density differences between boric acid and hydrocarbon phase. IN2002DE01134 further mentions that boric acid oxidations result in a large amount of by-products (acids/esters/carboxyl compounds) making separation and isolation difficult.

GB1183511 discloses a process for the production of alcohols by subjecting normal saturated hydrocarbons having from 10 to 30 carbon atoms or mixtures thereof to oxidation with molecular-oxygen in the presence of a dehydrated form of ortho-boric acid, distilling unreacted hydrocarbon and a ketone containing fraction from the reaction mixture and recycling them to the oxidation step, hydrolyzing the reaction mixture residue and recovering alcohols there from. According to GB1183511, alcohols that are formed from boric acid oxidation of paraffins and are further ethoxylated and used as detergents tend to bloom or discolour upon spray drying which interferes with general use.

An alternative process for preparing alcohols is disclosed in US6548718. In US6548718, either saturated or unsaturated aliphatic hydrocarbons are hydroxylated directly to the corresponding alcohol in the presence of a catalyst using N₂0 as the oxidant. Where the process of

US6548718 is used to convert olefins to alcohols, the obtained alcohols are inevitably unsaturated alcohols, comprising one or more double bonds. These unsaturated alcohols are less suitable for the above described applications such as detergents and chemically enhanced oil recovery. Irrespective of the starting material, i.e. either a paraffinic feedstock or olefinic feedstock, the process of US6548718 may be expected to produce a mixture of mono-, di- and higher substituted

hydrocarbons. This is mainly due to the presence of the catalyst, which is needed to be highly active to allow direct hydroxylation of the paraffins, but in return makes it difficult to control the degree of

hydroxylation, i.e. mono-, di, or higher substitution. There is a need in the art for a process for making secondary alcohols and derivatives thereof by a process having a reduced complexity, which omits the need for a catalyst .

Summary of the Invention

It has now been found that CIO to C30 alcohols may be prepared from their corresponding olefins by a non- catalytic oxidation with N₂0.

Accordingly, the present invention provides a process for preparing CIO to C30 alcohols, comprising the following steps :

(i) reacting aliphatic, non-cyclic CIO to C30

olefins with N₂0 to obtain an oxidation reaction product comprising CIO to C30 carbonyls;

(ii) reducing at least part of the CIO to C30

carbonyls in the oxidation reaction product to the corresponding CIO to C30 alcohols,

wherein the aliphatic, non-cyclic CIO to C30 olefins are reacted with the N₂0 in step (i) by:

(i-a) providing a liquid olefin feed comprising

aliphatic, non-cyclic CIO to C30 olefins;

(i-b) providing an oxidant feed comprising at least

5% by volume of N₂0, based on the total oxidant feed; and

(i-c) contacting the liquid olefin feed and the

oxidant feed with a porous material in a reactor at a temperature in the range of from 150 to 500° C and a pressure in the range of from 10 to 300 bar.

The process according to the present invention is particularly useful to prepare secondary alcohols from secondary olefins. The process according to the present invention is particularly useful to prepare saturated alcohols, i.e. not comprising double bonds, more

particularly saturated mono-alcohols .

The process according to the present invention has the advantage that is non-catalytic, thus omitting the need to use and replenish an expensive boric acid catalyst .

Furthermore, the process is less complex compared to prior art processes, requiring significantly less changes cooling/reheating cycles of the reaction mixture.

In the process of the present invention the

reactants, i.e. olefin and N₂0, are contacted

simultaneously with a porous material, whereby at least part of the reactants will enter the pores of the porous material. Contacting the reactants, i.e. olefin and N₂0, in the confinement of the pores of porous material may facilitate the intimate mixing of the reagents and increase conversion of the reactants to the desired products. The improved mixing of the reactants may also reduce the formation of by-products caused by the local accumulation of, in particular olefins, which may result in local non-stoichiometric mixtures of reactants.

In addition, the process according to the present invention uses N₂0 as an oxidant. N₂0 is a greenhouse gas, which is produced as a by-product of chemical processes such as processes for the production of adipic acid. In the process according to the invention the N₂0 is converted into nitrogen gas.

In another aspect the invention provides a process for producing surfactant compounds, comprising:

a) producing aliphatic, non-cyclic CIO to C30 alcohols according to the process for preparing CIO to C30 alcohols according to the invention;

b) reacting aliphatic, non-cyclic CIO to C30 alcohols with ethylene oxide or propylene oxide at temperature above 100°C and in the presence of a catalyst to produce ethoxylated or propoxylated alcohol surfactant compound.

In a further aspect the invention provides a method of treating a crude oil containing formation comprising admixing at least one of a CIO to C30 alcohol prepared according to the process for preparing CIO to C30 alcohols according to the invention and a surfactant compound prepared according to the process for preparing surfactant compounds according to the invention with water and/or brine, preferably from the formation from which crude oil is to be extracted, to form an injectable fluid and then injecting the injectable fluid into the formation .

Brief description of the drawings

Figure 1 provides a schematic representation of the calculated probability of the approach of adsorbed N₂0 and dodecene molecules within the pores of a zeolite.

Figure 2 provides a schematic representation of the calculated density of N₂0 and olefinic C=C bonds in a zeolite cell.

Detailed description of the invention

The present invention provides a process for

preparing aliphatic, non-cyclic CIO to C30 alcohols. The process may be used to prepare aliphatic, non-cyclic CIO to C30 primary alcohols; however the process according to the invention is particularly suitable for preparing secondary CIO to C30 alcohols as it allows for the production of secondary CIO to C30 alcohols in the absence of an oxidation catalyst. Preferably, the aliphatic, non-cyclic CIO to C30 alcohols are saturated alcohols. A particular advantage of the process according to the present invention is that is allows for the production of saturated aliphatic, non-cyclic CIO to C30 mono-alcohols. During the process, the N₂0 reacts with a mono-olefin at the double bond, to from a saturated mono- carbonyl, which subsequently is reduced to a saturated mono-alcohol. The process may therefore also be referred to as a process for making saturated CIO to C30 mono- alcohols. Preferably, an oxidation catalyst as referred to herein includes transitional metal-containing

materials such as transitional metal-containing metals, transitional metal-containing alloys, transitional metal- containing salts, transitional metal-containing metal oxides, transitional metal-containing metal complexes, transitional metal-containing heteropolyacids , in as such formulation or supported on solid carriers .

In the process according to the invention, (i) aliphatic, non-cyclic CIO to C30 olefins are directly oxidised with N₂0 to form CIO to C30 carbonyl compounds, in particular ketones and aldehydes, which are (ii) subsequently reduced to their corresponding alcohol.

Reference herein to CIO to C30 olefins is to one or more olefins comprising in the range of from 10 to 30 carbon atoms and mixtures thereof. Preferably, the aliphatic, non-cyclic CIO to C30 olefins reacted, i.e. oxidised, with the N₂0 in the absence of an oxidation catalyst.

In the process according to the present invention, aliphatic, non-cyclic CIO to C30 olefins are directly oxidised with N₂0 by contacting a liquid olefin feed comprising the olefins and an oxidant feed comprising the N₂0 in a reactor, wherein the non-cyclic CIO to C30 olefins and N₂0 are contacted with a porous material. Preferably, the liquid olefin feed comprising the olefins and an oxidant feed comprising the N₂0 are passed through a bed comprising the porous material or alternatively, but equally preferred by providing a slurry of the liquid olefin feed comprising the olefins, oxidant feed

comprising the N₂0 and the porous material. By providing a porous material in the reactor, the intimate mixing of the reactants is facilitated, in particular as the reactants pass, i.e. diffuse, absorb or otherwise transfer, into the pores of the porous material. It is therefore preferred that in the process according to the invention at least part of the aliphatic, non-cyclic CIO to C30 olefins and the N₂0 pass into the porous material, preferably into the pores of the porous material.

Preferably, at least part of the olefin and N₂0 reactants pass into the pores of, and optionally through, the porous material and within the confinement of the pores are forced in close proximity of each other, in

particular at the interstices of pores. In the absence of an oxidation catalyst the likelihood of a reaction occurring significantly increased where the reactants are brought into close proximity of each other. Although, a similar effect may also be ascertained in the absence of a porous material by e.g. increasing pressure or

temperature at which the olefin feed and oxidant feed are contacted, such increase pressure and/or temperature may also induce the formation of by-product due to incomplete mixing and locally existing non-stoichiometric mixtures of reactants, while at the same time increase temperature and pressure requirements of the process and reactor design. The intimate mixing and limited space inside the confinement of the pores of the porous material, however, induce a more complete mixing and resulting higher yield and/or a reduced by-product make at lower temperatures and pressures.

The porous material is preferably a non-catalytic porous material, i.e. the material does not have a significant catalytic activity with respect to the direct oxidation of the olefin with the N₂0. A non-catalytic porous material may also be referred to as an inert porous material. As mentioned herein-above the presence of the porous material alone already provides a desired enhancement of the conversion, whereas the presence of a catalyst would lead to an increased likelihood for the undesired formation of di- and higher substituted olefins. Preferably, the porous material does not comprise substantial amounts of one or more transition metals, more preferably elements selected from the group consisting of ruthenium, rhodium, iron, magnesium, manganese, cobalt, copper, titanium, iridium, vanadium. Preferably, the porous material comprises, if any, less than 0.1 wt% total metal based the weight of the porous material, more preferably less than 0.01 wt%.

The porous material preferably has a pore volume in the range of from 0.2 to 1.0 cm³/g, preferably of from 0.2 to 0.3 cm³/g, as determined by ASTM D4641-12

"Standard Practice for Calculation of Pore size

distribution of Catalysts and Catalyst Carriers from Nitrogen Desorption Isotherms".

Preferably, the porous material comprises pores, whereby at least 90% of the pores has a diameter in the range of from 0.3 to 10.0 nm (1 nm being 1 x 10^~9 m) , based on the total number of pores. Wherein the diameter of pores are determined N₂ physisorption (ASTM D4365-95 (2008) "Standard test for determining Micropore volume and Zeolite Area of a Catalyst") .

Preferably, the porous material has an internal surface area of in the range of from 200 to 1000 m²/g, preferably 250 to 750 m²/g, as determined by ASTM D3663- 03 (2008) "Standard Test Method for Surface Area of Catalysts and Catalyst Carriers".

The porous material may be any suitable porous material, including porous structured or amorphous materials . Preferred porous materials are structured porous materials, such as molecular sieves although amorphous materials with a relatively narrow and mono-modal pore size distribution can be used.

Structured porous materials generally comprise a channel structure, whereby the channels may have one or more diameters based on the selected material. The molecular sieves employed herein preferably have in at least one dimensional direction a channel having an 8-, 10- or 12-ring structure and an average pore size, or channel dimension, in the range of from about 0.4 to 1.0 nm (1 nm being 1 x 10^~9 m) . Preferred molecular sieves are those having channels one dimensional direction with a channel dimension, or average pore size, of in the range of from 0.5 to 0.8 nm, particularly of from 0.53 to 0.73 nm, and particularly of from 0.53 to 0.55 nm (1 nm being 1 x 10^~9 m) .

Preferred molecular sieves are those having a pore volume in the range of from 0.2 to 0.3 cm³/g, as

determined by ASTM D4365-95 (2008) "Standard Test Method for Determining Micropore Volume and Zeolite Area of a Catalyst" .

The channels structure may be one-dimensional or multi-dimensional. Preferably, the channels intersect. Of particular preference are materials having a multi^¬ dimensional channel structure, wherein at least part of the channels intersect. Preferably, the porous materials are molecular sieves with a multi-dimensional channel structure. This is beneficial as it is believed that in particular at the interstices of these channels the reactants preferentially react to form the desired products .

When no intersecting channels exist, the preferred type of molecular sieves has a one dimensional channel structure, which is linked with small cages where N₂0 is accessible, but essentially inaccessible to the CIO to C30 olefin. Preferably, the cage has a dimension below 0.5 nm, more preferably below 0.4 nm (1 nm being 1 x 10^~9 m) .

One preferred class of molecular sieves to be used as the porous material are zeolites. Particularly, preferred zeolites channels formed by a ring structure having in the range of 8 to 12 members. Preferably, the zeolite has a high Silica to Alumina Ratio (SAR) . This is preferred as the alumina in the zeolite causes an increase of the acidity of the zeolite, which may lead to decomposition of the olefins and accompanying deposition of carbon or the formation of oligomer by-products at the reaction

temperatures. Therefore preferably, the zeolite has a SAR of at least 200, more preferably a SAR of at least 500, even more preferably a SAR of at least 1000, even more preferably a SAR of at least 5000.

Where the zeolite comprises, next to silica, boron or gallium oxides it is preferred that the silica to boron oxide (calculated as B₂0₃) ratio and/or silica to gallium oxide (calculated as Ga₂0₃) of at least 200, more

preferably a SAR of at least 500, even more preferably a SAR of at least 1000, even more preferably a SAR of at least 5000. The presence of both boron and gallium may give rise to an acidity of the zeolite, albeit less than aluminium .

In one embodiment of the invention the zeolites may be zeolites that were treated to suppress acidity.

Preferred zeolites are MFI, MEL, MTT, MRE, TON, MWW and MTW type zeolites, more preferably ZSM 5, ZSM 11, MCM 22, MCM 36, MCM 56, ZSM 12 and silicalite-1, silicalite- 2. As mentioned herein above the amorphous materials with a relatively narrow and mono-modal pore size distribution can also be used. A preferred amorphous material is amorphous silica, preferably an amorphous silica having a pore volume in the range of from 0.3 to

1.0 cm³/g, as determined by ASTM D4641-12 "Standard

Practice for Calculation of Pore size Distribution of Catalysts and Catalyst Carriers from Nitrogen Desorption Isotherms" .

In a particularly preferred embodiment of the invention the porous material is selected from

silicalite-1 and silicalite-2. Silicalite-1 (MFI) and silicalite-2 (MEL) comprise essentially no alumina.

Without wishing to be bound to any particular theory, it is believed that as the reactants enter the pores of the porous material they are adsorbed on the walls of the pores and diffuse along the length of the pores. The relative ratio of adsorbed olefins and N₂0 may be

influenced by the selection of the pressure and

temperature at which the reactants are contacted with the porous material. An increase herein in temperature is believed to shift this ratio in the direction of the olefin .

The porous material may be present in the reactor in any suitable form, including but not limited to

particles, spheres, monoliths or shaped particles such as rings. The porous material may be combined with other materials such as fillers, binders and support materials. The porous material may be present as solid dispersion (or slurry) , solid packing, a fixed bed or moving bed.

Preferably, a solid packing or fixed bed.

The oxidation of C2 to C8 cyclic and aromatic olefins to carbonyl compounds using N₂0 has been described in for instance WO03/078370 and US2008/0021247. In the present invention, CIO to C30 aliphatic, non-cyclic olefins may be, via a carbonyl intermediate, converted to CIO to C30 alcohols, preferably aliphatic, saturated, non-cyclic CIO to C30 alcohols. Reference herein to CIO to C30 alcohols is to one or more alcohols comprising in the range of from 10 to 30 carbon atoms or mixtures thereof. Reference herein to saturated alcohols is to alcohols that do not comprise an olefinic bond. Preferably, the CIO to C30 aliphatic, non-cyclic olefins are secondary olefins (also referred to as internal olefins) and the secondary olefins are converted to secondary alcohols, aliphatic, saturated, non-cyclic secondary CIO to C30 alcohols.

In the process of the present invention, CIO to C30 alcohols are prepared by providing (i-a) a liquid olefin feed comprising aliphatic, non-cyclic CIO to C30 olefins and (i-b) an oxidant feed comprising at least 5% by volume of N₂0, based on the total oxidant feed.

The liquid olefin feed preferably comprises

aliphatic, non-cyclic CIO to C30 secondary olefins. The advantage of providing a feedstock comprising secondary olefins is that the secondary olefins may be converted, via their corresponding ketones, to secondary alcohols, whereas the use of a feedstock comprising primary olefins inevitably leads to a mixture of primary and secondary alcohols. These secondary alcohols are particularly suitable as a starting material to produce secondary alcohol alkoxylates surfactant compounds and secondary alcohol alkoxysulfate , alkoxysulfonate or

alkoxycarboxylate surfactant compounds. Preferably, the liquid olefins feed comprises at least 50wt% of secondary olefins, based on the olefins in the liquid olefin feed, more preferably at least 75wt%, even more preferably 90wt% of secondary olefins based on the olefins in the liquid olefin feed. The remaining olefins in the olefinic feedstock may include primary olefins. Preferably, the liquid olefins feed comprises in the range of from 50 to 100wt% of secondary olefins, based on the olefins in the liquid olefin feed, more preferably in the range of from 75 to 100wt%, even more preferably 90 to 100wt% of secondary olefins based on the olefins in the liquid olefin feed.

In one preferred embodiment, the process according to the invention is a process for preparing CIO to C30 secondary alcohols, comprising the following steps:

(iii) reacting aliphatic, non-cyclic CIO to C30

secondary olefins with N₂0 to obtain an oxidation reaction product comprising CIO to C30 secondary carbonyls;

(iv) reducing at least part of the CIO to C30

secondary carbonyls in the oxidation reaction product to the corresponding CIO to C30 secondary alcohols,

wherein the aliphatic, non-cyclic CIO to C30 olefins are reacted with the N₂0 by in step (i) :

(i-a) providing a liquid olefin feed comprising

aliphatic, non-cyclic CIO to C30 secondary olefins ;

(i-b) providing an oxidant feed comprising at least

5% by volume of N₂0, based on the total oxidant feed; and

(i-c) contacting the liquid olefin feed and the

The liquid olefin feed may preferably further comprise compounds that may act as diluents. Preferably, the liquid olefin feed comprises at least one hydrocarbonaceous diluent. Preferably, the diluents are inert with respect to N₂0 under the reaction conditions of step (i-c) . The term inert herein refers to compounds which either do not react with N₂0 under the reaction conditions selected in (i-c) , or react to such a limited extent compared to the reaction of olefins with N₂0 that at most 15% by weight, preferably at most 10% by weight and more preferably at most 5% by weight, of their reaction product with N₂0 is present in the oxidation reaction product, based on the weight of the oxidation reaction product obtained from step (i) .

The at least one diluent may be any diluent that is inert as defined herein above, preferably, the diluent does not react at all with the N₂0. Particularly suitable diluents are paraffins, alcohols, ketones, aldehydes, and mixtures thereof. More particularly CIO to C30 paraffins, aliphatic CIO to C30 alcohols, aliphatic CIO to C30 ketones, aliphatic CIO to C30 aldehydes, and mixtures thereof. Preferably such diluents are obtained as part of the process according to the invention for producing CIO to C30 alcohols or as part of a process for preparing the liquid olefinic feed to the process. A particularly preferred diluent is a paraffinic diluent, more

preferably a CIO to C30 paraffinic diluent, still more preferably CIO to C30 non-cyclic paraffinic diluent.

Even more preferably a paraffinic diluent that was obtained as part of a process for preparing the liquid olefinic feed to the process.

Preferably, the liquid olefin feed comprises in the range of from 5 to 95wt% of aliphatic, non-cyclic CIO to

C30 olefins, more preferably of from 10 to 90wt%, even more preferably of from 10 to 80wt% of aliphatic, non- cyclic CIO to C30 olefins, based on the liquid olefin feed. Still more preferably, the liquid olefin feed comprises in the range of from 25 to 75wt%, preferably 50 to 75wt% of aliphatic, non-cyclic CIO to C30 olefins, based on the liquid olefin feed.

In a preferred embodiment, the liquid olefin feed comprises in the range of from 1 to 99wt% of aliphatic, non-cyclic CIO to C20 olefins, more preferably C12 to C18 olefins, based on the olefins in the liquid olefin feed. Any resulting alcohol and/or surfactant compound prepared from CIO to C20, preferably C12 to C18 olefins are particularly suitable for detergent and personal care applications. More preferably, the liquid olefin feed comprises in the range of from 5 to 95wt%, even more preferably 10 to 90wt%, still more preferably of from 10 to 80wt% of aliphatic, non-cyclic C12 to C20 olefins, more preferably C12 to C18 olefins, based on the olefins in liquid olefin feed. Still even more preferably, the C12 to C20 olefins, preferably C12 to C18 olefins, are secondary olefins.

In another preferred embodiment, the liquid olefin feed comprises in the range of from 1 to 99wt% of aliphatic, non-cyclic C20 to C30 olefins, based on the olefins in the liquid olefin feed. Any resulting alcohol and/or surfactant compound prepared from C20 to C30 olefins are particularly suitable for chemically enhanced oil recovery applications. More preferably, the liquid olefin feed comprises in the range of from 5 to 95wt%, even more preferably 10 to 90wt%, still more preferably of from 10 to 80wt% of aliphatic, non-cyclic C20 to C30 olefins, based on the olefins in liquid olefin feed.

Still even more preferably, the C20 to C30 olefins are secondary olefins.

Preferred olefins are linear or low branched olefins. Where the olefins contain branching it is preferred that methyl branches represent between in the range of from 20% to 99% of the total number of branches present in the branched olefin. In some embodiments, methyl branches may represent greater than 50% of the total number of branches in the olefin. The number of ethyl branches in the alcohol may represent, in certain embodiments, less than 30% of the total number of branches. In other embodiments, the number of ethyl branches, if present, may be in the range of from 0.1% and 2% of the total number of branches. Branches other than methyl or ethyl, if present, may be less than 10% of the total number of branches. In some embodiments, less than about 0.5% of the total number of branches are neither ethyl or methyl groups. In an embodiment, an average number of branches per olefin molecule ranges from about 0 to about 2.5. In other embodiments, an average number of branches per alcohol ranges from about 0 to about 0.5.

Preferably, the liquid olefin feed as provided to the process comprises no more than 10wt%, more preferably no more than 5wt%, even more preferably no more than 1 wt% of di-olefins or higher unsaturated olefins. Di- olefins may lead to di- and higher alcohols, gum

formation and other undesired byproducts. Di-olefins may be removed prior to the reaction of the liquid olefin feed with the oxidant feed, e.g. by selectively

hydrogenating the di-olefins or higher unsaturated olefins in the liquid olefin feed to mono-olefins .

Preferably, the liquid olefin feed as provided to the process comprises no more than 10wt%, more preferably no more than 5wt%, even more preferably no more than 1 wt% of non-hydrocarbonaceous compounds, such as water.

The oxidant feed may be pure N₂0 or a mixture of N₂0 with one or more diluents. The oxidant feed may be provided as a gaseous, liquid or supercritical feed, preferably a gaseous or supercritical feed. The oxidant feed comprises at least 5% by volume of N₂0, based on the total oxidant feed. The reference herein to the

composition of the oxidant feed is to the composition as determined at ambient pressure and temperature (1 bar,

25°C) . By providing at least 5% by volume of N₂0, sufficient oxidant is provided to sustain the oxidation reaction and ensure sufficient conversion. Although, an oxidant feed consisting of pure N₂0 could be used, it is preferred to add a diluent to reduce the risk of forming an explosive mixture. In addition, introducing the oxidant at a molar ratio of N₂0 to olefin double bond in the range of from 0.5 to 5, preferably of from 0.6 to 1.5, more preferably 0.9 to 1.1, is preferred to increase selectivity of the reaction. Reference herein in to olefin double bonds is to the moiety of double bonds in the liquid olefin feed introduced to the process in step (i-a) . More preferably, the process of step (i) is N₂0 lean, i.e. the molar ratio of N₂0 to olefin double bond is below 1, to ensure most if not all of the N₂0 is consumed and little to no N₂0 remains in the oxidation reaction product. This would be undesired in view of the subsequent carbonyl reduction step (ii) to form the alcohol .

Preferably, the oxidant feed comprises in the range of from 5 to 35% by volume of N₂0, based on the volume of the oxidant feed. More preferably, the oxidant feed comprises in the range of from 7 to 20% by volume of N₂0, based on the volume of the oxidant feed.

As mention above preferably the oxidant feed

comprises a diluent, more preferably an inert diluent. The term "inert gas" as used herein refers to diluents which, with regard to the reaction of N₂0 with the olefins in the liquid olefin feed, behave inertly. Suitable inert diluents include, for example, nitrogen, carbon dioxide, carbon monoxide, argon, methane, ethane and propane .

Although not particularly preferred, the oxidant feed may also comprise diluent compounds, i.e. other than N₂0, that are not inert, such as oxygen. However, in case compounds, other than N₂0, which are not inert are present in the diluent, preferably the oxidant feed comprises at most 0.5% by volume, based on the volume of the oxidant mixture, of compounds, other than N₂0, that are not inert .

In the process according to the present invention, the liquid olefin feed is contacted with the oxidant feed in a reactor in the presence of a porous material to obtain an oxidation reaction product comprising CIO to

C30 carbonyls, including ketones and aldehydes. Reference herein to CIO to C30 carbonyls is to one or more

carbonyls comprising in the range of from 10 to 30 carbon atoms or mixtures thereof. During the contacting of the liquid olefin feedstock with the oxidant feedstock the

N₂0 reacts with the double bond of the olefin to form a ketone or aldehyde and N₂. Where the olefin is a

secondary olefin, predominantly ketones will be formed. In case of primary olefins a mixture of ketones and aldehydes are formed. Where the reaction takes place at the double bond, saturated ketones and aldehydes are formed. In the absence of a catalyst, the formation of unsaturated ketones and aldehydes is energetically unfavourable. Converting the olefins to saturated carbonyls is preferred. Preferably, the oxidation reaction product will comprise in the range of from 70 to 100 wt% of ketones, based on the carbonyls in the oxidation mixture. More preferably, the oxidation reaction product will comprise in the range of from 90 to 100 wt% of ketones, based on the carbonyls in the oxidation mixture. The content of ketones in the

oxidation reaction product will be largely driven by the secondary olefin content in the olefin feed. A high ketone content in the oxidation reaction product is preferred as these can conveniently be converted into the particularly preferred secondary alcohols .

The position of the carbonyl group along length of the hydrocarbon chain is determined by the position of the double bond. As the presence of a catalyst may result in the undesired formation of hydroxylate groups at other positions along length of the hydrocarbon chain, due to the direct hydroxylation of non-olefinic carbon atoms in the olefin, such as for instance described in US6548718, it is preferred that the liquid olefin feed is reacted with the oxidant feed in the absence of a catalyst.

The liquid olefin feed and the oxidant feed are contacted, with each other and the porous material, at temperatures in the range of from 150 to 500°C.

Preferably, at temperatures in the range of from 150 to

350°C, more preferably 180 to 350°C. It is preferred maintain the temperature equal to or below 350 °C as a higher temperature, the amount of N₂0 adsorbed in the pores may decease below a desirable level, thereby reducing the obtained extent of conversion.

The liquid olefin feed and the oxidant feed are contacted, with each other and the porous material, at pressures in the range of from 10 to 300 bar, preferably in the range from 10 to 250 bar and more preferably in the range from 25 to 250 bar. Reference herein to the unit "bar" is to "bar absolute", unless mentioned otherwise .

Preferably, the conditions under which the liquid olefin feed and the oxidant feed are contacted are chosen such that the liquid olefin feed remains liquid or supercritical during step (i) . Evaporation of the olefins in the liquid olefin feed is disadvantageous as the reaction between the olefin and the N₂0 is less selective when the olefins are in the gas phase.

The oxidant feed may be contacted with the liquid olefins feed by any means for contacting, including mixing, dispersing or dissolving the oxidant feed with or within the liquid olefin feed. The oxidant feed may be provided at once or a staged feeding of the oxidant feed may be applied. In the later case, the oxidant feed may be provided at several stages during step (i) of the process. This has the advantage that the N₂0

concentration at any time during step (i) may be

maintained at a lower level compared the concentration of

N₂0 that would be attained when the whole of the oxidant feed is contacted with the liquid olefin feed at the start of step (i), while the total amount of N₂0 provided during the process remains the same or may even be increased.

In one preferred embodiment, the oxidant feed is combined with the liquid olefin feed prior to step (i) at temperatures below 150°C, preferably below 100°C.

Preferably, the oxidant feed is combined with the liquid olefin feed at elevated pressure, more preferably pressures in the range of from 1.1 to 300 bar, more preferably 10 to 250, even more preferably the same pressure as the pressure at which the liquid olefin feed and oxidant feed are contacted in step (i-c) . The oxidant feed may be combined with the liquid olefin feed by mixing at least part of the oxidant feed with the liquid olefin feed, by dispersing at least part of the oxidant feed in the liquid olefin feed or by dissolving at least part of the oxidant feed in the liquid olefin feed. In another embodiment, the liquid olefin feed and oxidant feed are not combined prior to step (i), however the liquid olefin feed is preheated prior to contacting with the oxidant feed. Preferably, the liquid olefin feed is preheated to a temperature in the range of from 25 to

320°C, more preferably 150 to 320°C.

Where, the liquid olefin feed and/or the oxidant are introduced at a temperature below the desired reaction temperature of step (i) , it is preferred to increase the temperature in step (i) gradually, more preferably in the range of from 1 to 10°C/min, preferably of from 1.5 to 5°C/min and more preferably of from 2 to 4°C/min.

The reaction of step (i) may be performed in any suitable way, including batch-wise, as a semi-continuous or continuous process. Preferably, the process is operated as a continuous process. Examples of suitable continuous processes would include the use of continuous stirred tank reactors or tubular reactor. Most preferred is to operate the process in a continuous mode under plug-flow conditions in a tubular, or multi-tubular, reactor. The process may be operated in one or more reactors or reactor stages operated either in series or in parallel. Where a staged feeding to the oxidant feed is preferred this may include feeding separate fractions of the oxidant feed to one or more reactors or reactor stages. Where the process is operated with a liquid slurry comprising the liquid olefin feedstock, the oxidant feedstock, the porous material and, consequently, reactants, means may be provided to separate the porous material from the liquid effluent of the reactor. Such separation means are well known in the art for separating solids from liquids and include, but are not limited to, filtration and centrifugal separation. The oxidation reaction product obtained in step (i) will contain carbonyl compounds, in particular CIO to C30 carbonyls, more in particular saturated CIO to C30 carbonyls. Where the liquid olefin feed comprised predominantly C12 to C30 olefins, respectively C12 to C18 olefins, the oxidation reaction product will comprise predominantly C12 to C30 carbonyls, respectively C12 to C18 carbonyls. In the process according to the invention, the carbonyls in the oxidation reaction product are converted to alcohols (step (ii)) . The ketones are primarily reduced to secondary alcohols, whereas the aldehydes are primarily converted to primary alcohols. The carbonyls are converted to alcohols by reducing the carbonyl group to form an hydroxyl group. Preferably, the reduction of the carbonyl to its corresponding alcohol is done in the presence of a hydrogenation catalyst and hydrogen. Examples of suitable hydrogenation catalysts include Ni/Al₂0₃, and catalyst including CoMo, NiMo, W, Cu, Pt or Pd metals on silica, alumina, zirconia, titania comprising supports. Preferably, the carbonyls in the oxidation reaction product are reduced in the presence of the hydrogenation catalyst and hydrogen at temperatures in the range of from 50 to 140°C, more preferably of from 75 to 130°C, and pressures in the range of from 50 to 100 bar. The reduction of the carbonyls in the oxidation reaction mixture may be done batch wise, or in a semi- continuous or continuous manner. Preferably, the

reduction of the carbonyls in the oxidation reaction mixture is done continuously. It is a particular

advantage of the present invention that the carbonyl reduction of step (ii) is performed at a temperature below that of step (i) . As such there is no need to reheat the oxidation reaction product, while at the same time the oxidation reaction product may be used to preheat the liquid olefin feed and/or the oxidant feed being provided to step (i) , in order to cool the

oxidation reaction product to the temperature preferred for step (iv) . Optionally, additional cooling is applied to further cool the oxidation reaction product. This may again be done by heat exchange with other reactant or product streams or by other means.

Part or all of the oxidation reaction product may be provided to step (ii) . The oxidation reaction mixture may comprise in addition to the desired carbonyls, unreacted olefin and diluents. It will also comprise nitrogen.

Optionally, nitrogen is removed prior to step (ii) , e.g. by flashing. If desired the carbonyls may be separated from the remainder of the compounds in oxidation reaction product prior to step (ii) of the process. An advantage of providing at least the hydrocarbonaceous compounds, i.e. e.g. hydrocarbons and carbonyls, in the oxidation reaction product to step (ii) is that there is no need to first separate these components, which may require additional cooling and subsequent reheating steps.

Furthermore, separation the alcohols obtained in step (ii) from the remaining hydrocarbons may be energetically advantageous compared to separating the carbonyls from the oxidation reaction product.

Any unreacted olefin and diluents may be recycled to step (i) of the process according to the invention. The recycled diluents may comprise carbonyls and/or alcohols prepared in one or more steps of the process according to the invention. Such compounds are suitable diluents and, therefore, do not need to be removed. This has the advantage that not all carbonyls/alcohols need to be recovered following step (ii) , or where appropriate step (i) . This allows for the use of more energy benign and cheaper separation methods to recover the alcohol. Therefore in a preferred embodiment, a recycle comprising at least part of the unreacted olefin and diluent obtained in step (i) or step (ii) is provided to step (i) or to a process for producing olefins for the liquid olefin feed. Preferably, such recycle comprises in the range of from 0 to 10wt% of carbonyls and/or alcohols.

Where the diluent is a paraffinic diluent it may alternatively be provided to a process for preparing olefins. Preferably, such a paraffinic diluent is selectively hydrogenated to remove any residual olefins.

The liquid olefin feed may comprise any suitable olefins, preferably secondary olefins. One preferred process for providing the olefins is by a paraffin dehydrogenation process, typically a catalytic paraffin dehydrogenation process. One example of a suitable paraffin dehydrogenation process is the UOP PACOL process. One advantage of the use of paraffin

dehydrogenation processes to provide at least part of the liquid olefin feed is the fact that such processes produce predominantly secondary olefins, which can conveniently be converted to secondary alcohols in the process according to the invention. Moreover, the effluent of such a process is typically a mixture of olefin and unconverted paraffin. Such a mixture could be used directly as liquid olefin feed to step (i-a) of the process, whereby the paraffin acts as diluent.

A further advantage of use of paraffin

dehydrogenation processes to provide at least part of the liquid olefin feed is that as a by-product hydrogen is produced, which may preferably be used in step (ii) of the process to reduce the carbonyls in the oxidation reaction product to alcohols.

Therefore, preferably, step (i-a) of the process comprises providing a liquid olefin feed comprising aliphatic, non-cyclic CIO to C30 olefins, which liquid olefin feed was prepared by the catalytic dehydrogenation of a paraffin feedstock. Preferably, such liquid olefin feedstock prepared by the catalytic dehydrogenation process comprises aliphatic, non-cyclic olefins and paraffins, more preferably in the range of from 5 to 95wt% of aliphatic, non-cyclic CIO to C30 olefins, more preferably of from 10 to 90wt%, even more preferably of from 10 to 80wt% of aliphatic, non-cyclic CIO to C30 olefins, based on the liquid olefin feed. Still more preferably, the liquid olefin feed comprises in the range of from 25 to 75wt%, preferably 50 to 75wt% of aliphatic, non-cyclic CIO to C30 olefins, based on the liquid olefin feed. Preferably, the paraffin feedstock subjected to the catalytic dehydrogenation comprises CIO to C30 paraffins.

Reference herein to CIO to C30 paraffins is to one or more paraffins comprising in the range of from 10 to 30 carbon atoms or mixtures thereof.

An alternative process for providing the olefins is by an ethylene oligomerisaton process. One such process is the Shell SHOP process. Ethylene oligomerisaton processes typically produces predominantly primary olefins. As mentioned above, preferred liquid olefin feeds comprise significant amounts of secondary olefins. Therefore, it is preferred to isomerise at least part of the primary olefins obtained from an ethylene

oligomerization process to secondary olefins. The secondary olefins that are used to make the secondary alcohols olefin sulfonates of the present invention may be made by skeletal isomerization . Suitable processes for making the secondary olefins from the primary olefins include those described in US5510306, US5633422,

US5648584, US5648585, US5849960, and EP0830315 Bl, all of which are herein incorporated by reference in their entirety .

The N₂0 in the oxidant feed may be any available N₂0. The N₂0 may be produced purposely for the process

according to the invention, e.g. by thermally decomposing ammonium nitrate at a temperature of approximately 250°C. Alternatively, the N₂0 can be prepared by the catalytic oxidation of ammonia. However, preferably the N₂0 is obtained as a by-product from a commercial nitrogen chemistry manufacturing processes, including, but not limited to, processes for the production of dodecanedioic acid, hydroxylamine and nitric acid manufacture. A particularly preferred source of N₂0 is a process for producing adipic acid. It is envisaged that the N₂0 by- product from one world scale adipic acid plant, would be sufficient to produce in the range of 400-500 kta of CIO to C30 alcohols.

In a further aspect the present invention provides a process for producing surfactant compounds. The process for producing surfactant compounds includes producing alcohols according to the process for producing CIO to C30 alcohols according to the invention.

The alcohols may be directly sulfonated, sulfated or carboxylated to produce surfactant compounds. However, preferably, the alcohols are first ethoxylated and/or propoxylated, further referred to as alkoxylated. Such alkoxylated alcohols (or alcohol alkoxylate) may be used as surfactant compounds, but may also be sulfonated, sulfated or carboxylated to produce further surfactant compounds

The alcohols may be alkoxylated by reacting them with ethylene oxide (EO) and/or propylene oxide (PO) in the presence of an appropriate alkoxylation catalyst. The alkoxylation catalyst may be sodium hydroxide which is commonly used commercially for alkoxylating alcohols. The alcohols may be alkoxylated using a double metal cyanide catalyst as described in US6977236 which is herein incorporated by reference in its entirety. The alcohols may also be alkoxylated using a lanthanum-based or a rare earth metal-based alkoxylation catalyst as described in US5059719 and US5057627, both of which are herein incorporated by reference in their entirety.

The alcohol alkoxylates may be prepared by adding to the alcohols a calculated amount, for example in the range of from 0.1 wt% to 0.6 wt%, of a strong base, typically an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide or potassium

hydroxide, which serves as a catalyst for alkoxylation.

An amount of ethylene oxide and/or propylene oxide calculated to provide the desired number of moles of ethylene oxide or propylene oxide per mole of alcohol is then introduced and the resulting mixture is allowed to react until the alkoxy compounds are consumed. Suitable reaction temperatures are typically above 100°C,

preferably in the range of from 120 to 220°C.

The alcohol alkoxylates of the present invention may be prepared by using a multi-metal cyanide catalyst as the alkoxylation catalyst. The catalyst may be contacted with the alcohol and then both may be contacted with the ethylene or propylene oxide reactant which may be introduced in gaseous form. Preferably, elevated pressure is used to maintain the alcohol substantially in the liquid state.

It should be understood that the alkoxylation procedure serves to introduce a desired average number of ethylene oxide and/or propylene oxide units per mole of alcohol. For example, treatment of an alcohol with 1.5 moles of propylene oxide per mole of alcohol serves to effect the propoxylation of each alcohol molecule with an average of 1.5 propylene oxide moieties per mole of alcohol moiety, although a substantial proportion of alcohol moieties will have become combined with more than 1.5 propylene oxide moieties and an approximately equal proportion will have become combined with less than 1.5. In a typical alkoxylation product mixture, there is also a minor proportion of unreacted alcohol. Preferably, in the range of from 1 to 10 alkoxy groups are reacted per alcohol. These alkoxylated alcohols are suitable surfactant compounds .

In the preparation of the sulfonates derived from the alkoxylated alcohols of the present invention, the alkoxylates are reacted with epichlorohydrin, preferably in the presence of a catalyst such as tin tetrachloride at an elevated temperature, preferably in the range of from 110 to 120 °C for in the range of from 3 to 5 hours at a pressure of in the range of from 1 to 1.1 bar in toluene. Next, the reaction product is reacted with a base such as sodium hydroxide or potassium hydroxide at elevated temperature, preferably in the range of from 85 to 95 °C for in the range of from 2 to 4 hours at a pressure of in the range of from 1 to 1.1 bar. The reaction mixture is cooled and separated in two layers. The organic layer is separated and the product isolated. It is then reacted with sodium bisulfite and sodium sulfite at an elevated temperature, preferably in the range of from 140 to 160°C for in the range of from 3 to

5 hours at an elevated pressure, preferably in the range of from 4 to 5.5 bar. The reaction is cooled and the product sulfonate is recovered as about a 25 wt% alcohol alkoxysulfonate solution in water. The alcohol alkoxylates may be sulfated using one of a number of sulfating agents including sulfur trioxide, complexes of sulfur trioxide with (Lewis ) bases , such as the sulfur trioxide pyridine complex and the sulfur trioxide trimethylamine complex, chlorosulfonic acid and sulfamic acid. The sulfation may be carried out at a temperature preferably not above 80°C. The sulfation may be carried out at temperature as low as -20°C, but higher temperatures are more economical. For example, the sulfation may be carried out at a temperature in the range of from 20 to 70°C, preferably of from 20 to 60°C, and more preferably of from 20 to 50°C. Sulfur trioxide is the most economical sulfating agent.

The alcohol alkoxylates may be reacted with a gas mixture which in addition to at least one inert gas contains in the range of 1 to 8 percent by volume, relative to the gas mixture, of gaseous sulfur trioxide, preferably in the range of from 1.5 to 5 percent volume. In principle, it is possible to use gas mixtures having less than 1 percent by volume of sulfur trioxide but the space-time yield is then decreased unnecessarily. Inert gas mixtures having more than 8 percent by volume of sulfur trioxide in general may lead to difficulties due to uneven sulfation, lack of consistent temperature and increasing formation of undesired by-products. Although other inert gases are also suitable, air or nitrogen are preferred, as a rule because of easy availability.

The reaction of the alcohol alkoxylate with the sulfur trioxide containing inert gas may be carried out in falling film reactors. Such reactors utilize a liquid film trickling in a thin layer on a cooled wall which is brought into contact in a continuous current with the gas. Kettle cascades, for example, would be suitable as possible reactors. Other reactors include stirred tank reactors, which may be employed if the sulfation is carried out using sulfamic acid or a complex of sulfur trioxide and a (Lewis) base, such as the sulfur trioxide pyridine complex or the sulfur trioxide trimethylamine complex. These sulfation agents would allow an increased residence time of sulfation without the risk of

ethoxylate chain degradation and olefin elimination by (Lewis) acid catalysis.

The molar ratio of sulfur trioxide to alkoxylate may be 1.4 to 0.8, preferably 1.0 to 0.8. Sulfur trioxide may be used to sulfate the alkoxylates and the temperature may in the range of from -20 °C to 50 °C, preferably of from 5 °C to 40 °C, and the pressure may be in the range from 1 to 5 bar. The reaction may be carried out continuously or discontinuously . The residence time for sulfation may range from 0.5 seconds to 10 hours, but is preferably from 0.5 seconds to 20 minutes.

The sulfation may be carried out using

chlorosulfonic acid at a temperature from -20 C to 50

C, preferably from 0 C to 30 C. The mole ratio between the alkoxylate and the chlorosulfonic acid may range from about 1:0.8 to about 1:1.2, preferably about 1:0.8 to 1:1. The reaction may be carried out continuously or discontinuously for a time between fractions of seconds

(i.e., 0.5 seconds) to 20 minutes.

Unless they are only used to generate gaseous sulfur trioxide to be used in sulfation, the use of sulfuric acid and oleum should be omitted. Subjecting any

ethoxylate to these reagents leads to ether bond breaking

- expulsion of 1,4-dioxane (back-biting) - and finally conversion of alcohol to an internal olefin. Following sulfation, the liquid reaction mixture may be neutralized using an aqueous alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, an aqueous alkaline earth metal hydroxide, such as magnesium hydroxide or calcium hydroxide, or bases such as ammonium hydroxide, substituted ammonium hydroxide, sodium carbonate or potassium hydrogen carbonate. The

neutralization procedure may be carried out over a wide range of temperatures and pressures. For example, the neutralization procedure may be carried out at a

temperature in the range of from 0 C to 65°C and a pressure in the range of from 1 to about 2 bar. The neutralization time may be in the range of from 0.5 hours to 1 hour but shorter and longer times may be used where appropriate. The alcohol alkoxysulfates and alcohol alkoxysufonates thus produced are suitable surfactant compounds .

The alkoxylated alcohols of this invention may be carboxylated by any of a number of well-known methods. It may be reacted with a halogenated carboxylic acid to make a carboxylic acid. Alternatively, the alcoholic end group - CH₂OH - may be oxidized to yield a carboxylic acid. In either case, the resulting carboxylic acid may then be neutralized with an alkali metal base to form a carboxylate surfactant .

In a specific example, an alkoxylated alcohol may be reacted with potassium t-butoxide and initially heated at, for example, 60°C under reduced pressure for, for example, 10 hours. It would be allowed to cool and then sodium chloroacetate would be added to the mixture. The reaction temperature would be increased to, for example, 90°C under reduced pressure for, for example, 20 to 21 hours . It would be cooled to room temperature and water and hydrochloric acid added. This would be heated to, for example, 90 °C for, for example, 2 hours. The organic layer may be extracted by adding ethyl acetate and washing it with water .

The alcohol alkoxycarboxylates thus produced are suitable surfactant compounds.

The alcohol sulfates and sulfonates, alkoxylated alcohols, alcohol alkoxysulfate and alcohol

alkoxysufonate as well as the alcohol alkoxycarboxylates surfactant compounds produced using the process for producing surfactant compounds are preferably secondary alcohol sulfates and sulfonates, alkoxylated secondary alcohols, secondary alcohol alkoxysulfate and secondary alcohol alkoxysufonate as well as secondary alcohol alkoxycarboxylates surfactant compounds. These secondary alcohol based surfactants may be obtained by the process of the present invention, by using secondary olefins as the olefins in the liquid olefin feedstock.

The surfactant compounds herein described have better biodegradability compared to established alkyl benzene based surfactants, while the secondary alcohol based surfactant tend to outperform their primary based alcohol counterparts with respect to e.g. surface tension reduction. These surfactant compounds may be used to produce household detergents including laundry powders, laundry liquids, dishwashing liquids and other household cleaners, as well as lubricants and personal care compositions .

One particular suitable application of the alcohols and surfactant compounds prepared by the processes of the present invention is chemically enhanced oil recovery, wherein a crude oil reservoir is treated with at least one of the alcohol or surfactant compounds prepared by the processes of the present invention to enable the recovery of crude oil from the reservoir.

In a further aspect the invention therefore provides a method of treating a crude oil containing formation comprising admixing at least one of a CIO to C30 alcohol prepared according to the process for preparing CIO to C30 alcohols according to the invention and a surfactant compound prepared according the process for preparing surfactant compounds according to the invention with water and/or brine, preferably from the formation from which crude oil is to be extracted, to form an injectable fluid and then injecting the injectable fluid into the formation. Preferred alcohols and surfactant compounds for use in such method of treating a crude oil containing formation are those that were prepared from a liquid olefin feed comprising in particular C20 to C30 olefins, more preferably C20 to C30 secondary olefins.

In chemically enhanced oil recovery (cEOR)

applications, surface active compounds are provided to the reservoir to improve mobilization of the

hydrocarbons. A class of surface active compounds, or surfactants, that is particularly suitable for cEOR application are secondary (also referred as internal) olefin sulfonates. Secondary olefin sulfonates are chemically suitable for EOR because they have a low tendency to form ordered structures/liquid crystals (which can be a major issue because long range ordered molecular structuring tends to dramatically increase fluid viscosities and can to lead decreased mobility of fluids within the hydrocarbon formations, and reduced recoveries) because they are a complex mixture of surfactants with different chain lengths. Secondary olefin sulfonates show a low tendency to adsorb on reservoir rock surfaces arising from negative-negative charge repulsion between the surface and the surfactant.

The alcohols and surfactant compounds, optionally together with other components in a thus formed

hydrocarbon recovery composition, may interact with hydrocarbons in at least a portion of a hydrocarbon containing formation. Interaction with the hydrocarbons may reduce interfacial tension of the hydrocarbons with one or more fluids in the hydrocarbon containing

formation. In other embodiments, alcohols and surfactant compounds may reduce the interfacial tension between the hydrocarbons and an overburden/underburden of a

hydrocarbon containing formation. Reduction of the interfacial tension may allow at least a portion of the hydrocarbons to mobilize through the hydrocarbon

containing formation.

The method of treating a crude oil containing formation preferably comprises admixing at least an alcohol and/or surfactant compound prepared according to a process according to the invention with water and/or brine from the formation from which crude oil is to be extracted to form an injectable fluid, wherein the alcohols and surfactant compounds comprises in the range of from 0.05 to 1.0 wt%, preferably in the range of from 0.1 to 0.8 wt% of the injectable fluid, and then

injecting the injectable fluid into the formation.

The interactions between the alcohols and surfactant compounds and the hydrocarbons in the hydrocarbon containing formation have been described in for instance WO2011/100301, which is incorporated herein by reference.

WO2011/100301 describes methods to determine the

suitability of different internal olefin sulfonates composition for a particular hydrocarbon containing formation . In an embodiment of a method to treat a hydrocarbon, preferably crude oil, containing formation, an internal olefin sulfonate composition may be provided (e.g. by injecting a fluid comprising the internal olefin

sulfonate composition) into a hydrocarbon containing formation through an injection well.

In an embodiment, an alcohols and/or surfactant compounds composition is provided to the formation containing crude oil with heavy components by admixing it with brine from the formation from which hydrocarbons are to be extracted or with fresh water. The mixture, i.e. the injectable fluid, is then injected into the

hydrocarbon containing formation.

In an embodiment, an alcohols and/or surfactant compounds composition may interact with at least a portion of hydrocarbons and at least a portion of one or more other fluids in the formation to reduce at least a portion of the interfacial tension between the

hydrocarbons and one or more fluids. Reduction of the interfacial tension may allow at least a portion of the hydrocarbons to form an emulsion with at least a portion of one or more fluids in the formation. An interfacial tension value between the hydrocarbons and one or more fluids may be altered by the internal olefin sulfonate composition to a value of less than 0.1 dyne/cm. In some embodiments, an interfacial tension value between the hydrocarbons and other fluids in a formation may be reduced by the hydrocarbon recovery composition to be less than 0.05 dyne/cm. An interfacial tension value between hydrocarbons and other fluids in a formation may be lowered by the internal olefin sulfonate composition to less than 0.001 dyne/cm, in other embodiments. At least a portion of the alcohols and/or surfactant compounds composition/hydrocarbon/fluids mixture may be mobilized to a production well.

An increased hydrocarbon mobility and consequently increased hydrocarbon production may increase the economic viability of the hydrocarbon containing

formation .

Examples

Example 1.

Grand Canonical Monte Carlo simulations using the Materials Studio® molecular modeling platform from

Accelrys are used to study the adsorption of a mixture of N₂0 and 1-dodecene molecules in silicalite-1 at 50 bar and three temperatures: 250, 300 and 350°C for the purpose of comparison. The fixed-pressure calculations at each temperature give information about the average loading of each molecule in the adsorbent .

Table 1 shows the adsorption of pure N₂0, pure dodecene and a mixture of N20 and dodecene at a total pressure of 50 bar and 3 temperatures.

As can be seen from Table 1, both N₂0 and dodecene can be absorbed in the pores of the silicalite-1. Where a mixture N₂0 and dodecene is provided both reagents are simultaneously absorbed in the pores of the silicalite-1.

It is observed that an increase in temperature leads to an increase in the number of adsorbed dodecene molecules and a concomitant decrease in the population of adsorbed N20. Therefore, the relative proportions of adsorbed species may be tuned using temperature as a handle, thereby maintaining one of them as a limiting reactant.

Table 1.

(°C) Fraction Partial N₂0 C12* N₂0 + C12 (-)¹ Pressure

(bar) ¹

250 0.91 45 25 7 16 + 3

300 0.81 40 21 7 + 5

350 0.53 27 16 8 3 + 7

* The simulation of pure dodecene adsorption at 250 and 350°C showed little variance in the number of adsorbed molecules, no computation was performed at 300°C.

1 Total pressure is 50 bar, the N₂0 mole fraction and partial pressure are dictated by the vapor phase split of N₂0 & Ci2 at the corresponding temperature.

The results presented in Table 1 confirm that both reactants can be brought in close proximity in the confinement of the pores of the porous material.

This is supported by the results presented in Figure 1, wherein the calculated probability of the adsorbed N₂0 and dodecene molecules approaching each other within the pores of the zeolite is represented. There is a finite probability of the proposed reaction centers, i.e., the C=C double bond and the N₂0, coming within approximately 0.2 x 10^~9m of each other, i.e. after including the van der Waal radii of the C and 0 atoms. It is observed that the probability of closest-approach, and hence the likelihood of reaction, decreases with increasing temperature due to the lower population of N₂0 adsorbed in the silicalite-1 at higher temperature.

In Figure 2, density calculations are represented in density maps, showing concentrations of N₂0 in density maps 2 (a) -(d) and the concentration of the olefinic C=C bonds in density maps 2(e) -(h) for a zeolite cell. Each density map, i.e. (a) - (d) and respectively (e) to (h) , shows the density of the reactants in four different sections of the silicalite-1 taken along the OB-axis. The OB axis is the y-axis where 0, the origin is located at one vertex of the zeolite. The height of the zeolite cell along the y-axis is approximately 20 Angstroms (A) and 4 slices were taken, each 5 A thick. Figure 2 shows the density maps for each of the four slices for a Molecular Dynamics run conducted at 50 bar and at 250°C, whereby

Figure 2 (a) and (e) represent a first slice of the zeolite cell starting at 0 to a thickness of 5 A; Figure 2 (b) and (f) represent the second slice (5-10 A); Figure 2 (c), (g) the third slice (10-15 A); and Figure 2 (d) , (h) the last slice of the zeolite cell from 15-20 A.

As can be seen from Figure 2, the two reactants

congregate in the region where two channels of the silicalite-1 intersect. Example 2.

A 1-dodecene sample was oxidized using N₂0 to form corresponding carbonyls. 1-dodecene was chosen as a representative starting olefin for production of

detergent range alcohols. The oxidation was done using the following experimental set-up and procedure. A 100 cc stainless steel autoclave is loaded with 15g of 1- dodecene. Optionally, a predetermined amount of

silicalite-1 powder having a SAR of about 7500, a surface area more than 400 m²/g and a crystal size less than 0.1 ]im is added to the reactor as an inert porous material.

The reactor is subsequently sealed. The reactor is purged with nitrogen. The nitrous oxide (N₂0) oxidant is added at ambient temperature or at 40 °C and the reactor is pressurized by adding additional nitrogen. The

temperature is slowly increased to the reaction

temperature in about an hour while the reactants are continuously stirred with a gas-dispersion stirrer. The reaction is stirred at temperature for the duration of the experiment . At the end of the experiment the reactor is cooled, depressurized and purged with nitrogen. The reaction product is collected and filtered. The filtered liquid reaction product is analyzed via gas

chromatography (GC) . Conversion and yield are defined as:

Conversion (wt%) = olefin concentration in the feed

(wt%) - olefin concentration in product (wt%) ;

Yield (wt%) = Cll and C12 carbonyl concentration in product (wt%) .

Comparative Example 2a

15g of 1-dodecene, together with 12.07 bar (175 psig) of N₂0 and 4.14 bar (60 psig) of N₂, was heated to a heated temperature of 250°C while being stirred at 750 rpm. The mixture was maintained at the reaction

temperature for 7 hours. At the end of the experiment, the liquid reaction product was analyzed via GC and the results are provided in Table 2.

Example 2b (according to the invention)

15g of 1-dodecene, together with 0.5 g of silicalite-

1, 12.07 bar (175 psig) of N₂0 and 4.14 (60 psig) of N₂, was heated to a temperature of 250 °C while being stirred at 750 rpm and held at temperature for 7 hours.

The mixture was maintained at the reaction temperature for 7 hours. At the end of the experiment, the liquid reaction product was analyzed via GC and the results are provided in Table 2.

Example 2c (according to the invention)

15g of 1-dodecene, together with 2 g of silicalite-1,

12.07 bar (175 psig) of N₂0 and 4.14 (60 psig) of N₂, was heated to a temperature of 250 °C while being stirred at 750 rpm and held at temperature for 7 hours. The mixture was maintained at the reaction temperature for 7 hours. At the end of the experiment, the liquid reaction product was analyzed via GC and the results are provided in Table 2.

Example 2d (according to the invention)

15g of 1-dodecene, together with 4 g of silicalite-1,

As can be seen from Table 2, the presence of the inert porous material significantly reduces the formation of the by-product 1-decylcyclopropane, from 9 wt% in the absence of the inert porous material to below 1 wt% in the presence 4 grams of inert porous material. When using a primary olefin (also referred to as alpha-olefin or terminal olefin) as the starting material, approximately equal amounts of ketones and aldehydes are produced.

The ketones can be reduced, e.g. in the presence of the hydrogenation catalyst and hydrogen at hydrogenation temperatures, to secondary alcohols. The aldehydes can be similarly reduced to primary alcohols. Therefore, experiments 2b to 2d show that a mixture of secondary and primary alcohols may be produced, while the by-product formation is significantly reduced due to the presence of the inert porous material. Example 3

An internal dodecene sample was oxidized using N₂0 to form corresponding carbonyls. The internal dodecene was prepared by a double bond isomerisation of 1-dodecene to give an internal or secondary dodecene. The internal dodecene is a representative starting secondary olefin for production of detergent range secondary alcohols. The oxidation was done using the following experimental set^¬ up and procedure as described for Example 2.

Where an inert porous material was added the material was the same as for Example 2, i.e. a predetermined amount of silicalite-1 powder having a SAR of about 7500, a surface area more than 400 m2/g and a crystal size less than 0.1 μπι .

Similar to Example 2, conversion and yield are defined as :

Conversion (wt%) = olefin concentration in the feed (wt%) - olefin concentration in product (wt%) ; Yield (wt%) = Cll and C12 carbonyl concentration in product (wt%) .

Comparative example 3a

15g of internal dodecene, together with 22.41 bar (325 psig) of N₂0 and 4.14 bar (60 psig) of N₂, was heated to a temperature of 250°C while being stirred at 750 rpm. The mixture was maintained at the reaction temperature for 7 hours. At the end of the experiment, the liquid reaction product was analyzed via GC and the results are provided in Table 2.

Example 3b (according to the invention)

15g of internal dodecene, together with 4 g of silicalite-1, 22.41 bar (325 psig) of N₂0 and 4.14 bar (60 psig) of N₂, was heated to a temperature of 250°C while being stirred at 750 rpm. The mixture was

maintained at the reaction temperature for 7 hours. At the end of the experiment, the liquid reaction product was analyzed via GC and the results are provided in Table 2. When using an internal olefin as the starting material, the predominant product is a ketone. The ketones can be reduced, e.g. in the presence of the hydrogenation catalyst and hydrogen at hydrogenation temperatures, to secondary alcohols. By reacting the internal olefin with N₂0 in the presence of inert porous material the Cll and C12 carbonyl, i.e. ketones and aldehydes, yield is increased significantly compared to the comparative example where no inert porous material was present. Also the conversion is increased. The addition of the inert porous material allows for an efficient production of secondary alcohols from

secondary olefins.

Table 2.

*based on liquid reaction product

#obtained yield of both Cll and C12 carbonyls, i.e. ketones and aldehydes

Claims

C L A I M S

. A process for preparing CIO to C30 alcohols, comprising the following steps:

(i) reacting aliphatic, non-cyclic CIO to C30

(ii) reducing at least part of the CIO to C30

carbonyls in the oxidation reaction product to the corresponding CIO to C30 alcohols, wherein the aliphatic, non-cyclic CIO to C30 olefins are reacted with the N₂0 in step (i) by:

(i-a) providing a liquid olefin feed comprising

aliphatic, non-cyclic CIO to C30 olefins;

(i-b) providing an oxidant feed comprising at least

5% by volume of N₂0, based on the total oxidant feed; and

(i-c) contacting the liquid olefin feed and the

A process according to claim 1, wherein the liquid olefin feed comprises aliphatic, non-cyclic secondary CIO to C30 olefins .

A process according to claim 2, wherein the liquid olefin feed comprises in the range of from 90 to 100wt% of aliphatic, non-cyclic secondary CIO to C30 olefins, based on the olefins in the liquid feed.

The process according to any one of claims 1 to 3, wherein the liquid olefin feed further comprises at least one hydrocarbonaceous diluent which is inert toward N₂0 under the conditions of step (iii) .

5. A process according to any one of claims 1 to 4, wherein the porous material is a molecular sieve material.

6. A process according to any one of claims 1 to 5, wherein the porous material is a zeolite.

7. A process according to claim 6, wherein the zeolite has a SAR of at least 1000.

8. A process according to claim 6, wherein the zeolite is selected from the group consisting of silicalite-1 and silicalite-2.

9. A process according to any one of claims 1 to 8, wherein the aliphatic, non-cyclic CIO to C30 olefins are produced by a paraffin dehydrogenation process.

10. A process according to any one of claims 1 to 8, wherein the aliphatic, non-cyclic CIO to C30 olefins are produced by an ethylene oligomerization process to produce primary olefins followed by an isomerization of at least part of the primary olefins to secondary olefins.

11. A process according to any one of claims 1 to 10,

wherein the aliphatic, non-cyclic CIO to C30 olefins are reacted with the N₂0 in the absence of a catalyst.

12. A process for producing surfactant compounds,

comprising :

a) producing CIO to C30 alcohols according to any one of claims 1 to 11;

b) reacting the alcohols with ethylene oxide or propylene oxide at temperature above 100°C and in the presence of a catalyst to produce alkoxylated alcohol surfactant compounds .

13. A process according to claim 12, wherein the alkoxylated alcohols are sulfated or sulfonated to at least one surfactant component selected from alcohol alkoxysulfate and alcohol alkoxysulfonate . A process according to claim 12, wherein the alkoxylated alcohols are carboxylated to alcohol alkoxycarboxylates. A method of treating a crude oil containing formation, comprising admixing at least one of:

- a CIO to C30 alcohol prepared according to any one of claims 1 to 11; and/or

- a surfactant compound prepared according to any one of claim 12 to 14,

with water and/or brine to form an injectable fluid and then injecting the injectable fluid into the formation.