EP1812376A1

EP1812376A1 - Process for making long chain internal fatty tertiary amines

Info

Publication number: EP1812376A1
Application number: EP05810966A
Authority: EP
Inventors: Corey James Kenneally; Jeffrey John Scheibel
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 2004-11-15
Filing date: 2005-11-15
Publication date: 2007-08-01
Also published as: BRPI0518005A; CN101528664A; CA2586592A1; WO2006050994A1; JP2008519802A

Abstract

The invention relates to a process for preparing long chain internal fatty amines, quaternized amines and amine oxides and selected amine oxides having a symmetric alkyl portion.

Description

PROCESS FOR MAKING LONG CHAIN INTERNAL FATTY TERTIARY

AMINES

FIELD OF THE INVENTION The present invention relates to an aminomethylation process for making long chain internal fatty tertiary amine, quaternized amines and the corresponding amine oxides.

BACKGROUND OF THE INVENTION

Linear tertiary amines with chain lengths between 8 and 24 carbon atoms are com- monly referred to as fatty tertiary amines. According to Ullman's Encyclopedia of Chemical Technology, 5* edition, Volume Al, these materials, and their derivatives such as the corresponding quaternary ammonium compounds, are widely used in ap¬ plications such as fabric softeners, drilling muds, surfactants, asphalt emulsifiers, and bactericides/disinfectants.

For fabric softeners, the most effective are the fatty quaternary ammonium compounds dialkyldimethyl ammonium chloride or the corresponding methyl sulfate. For drilling muds, methyl or benzyl quaternary ammonium chlorides produced from dialkyl methyl amine are useful. For surfactants, C₁₂ or C₁₄ based dimethylalkyl amine oxide is commonly used. For bactericides and disinfectants, alkyl(benzyl)dimethyl and alky trimethyl compounds in which the fatty alkyl group contains 12 to 14 carbon atoms are most effective against a broad range of organisms. Alternatively, the dialkyl di¬ methyl compounds are most effective when the fatty alkyl group contains 8-10 carbon atoms.

Fatty amines are commonly produced from natural fats and oils or from conventional petrochemical raw materials. Three primary feedstocks are used to make fatty tertiary amines: fatty nitriles, fatty alcohols or aldehydes, and long chain olefins.

Fatty nitriles, which are formed from fatty acids and ammonia over dehydrating cata¬ lysts in liquid phase reactors or liquid and vapor-phase reactors at 280 to 360° C, are reacted either with dimethylamine or with formaldehyde and formic acid to produce N,N-dimethylalkylamines (see US 4,248,801 to Lion Fat & Oil Co. and US 3,444,205 to Hoechst). Fatty alcohols and aldehydes can be converted into the same product via direct amina- tion in the presence of dimethylamine or other primary or secondary amines at 230° C at atmospheric pressure (0.1 - 0.5 MPa) using copper chromite catalysts (for alcohol feedstocks) or noble metal, copper chelate, or copper carboxylate catalysts (for alde- hydes) (see US 4,251,465 to Gulf Research and Development Co., US 4,138,437 to Hoechst, and both US 4,254,060 and US 4,210,605 to Kao).

These processes, however, produce a high content of terminal amines, typically 91 wt% or greater. As used herein "terminal amines" means that the amine moiety is connected on a α or β carbon of the long chain alkyl chain of the amine.

For the case of amine oxide surfactants, this is done to provide good cleaning with high suds stability. However, sometimes it is desirable to produce with a high content (10 wt% or more) of internal amine. This would be useful for branched chain surfac- tants with improved cold water cleaning, moderate suds stability, and improved wet¬ ting properties.

Therefore, there is a need for a commercially feasible process for making long chain fatty tertiary amines and amine oxides which provide the desired content of internal amines, using hydrocarbons from a variety of sources. A secondary objective is to produce these amines via a low cost, economical process.

SUMMARY OF THE INVENTION

The present invention relates to a process comprising the steps of (a) providing a long chain internal olefin source selected from the group consisting of oligomerized C₂ to C₁₁ olefins, metathesized C₅ to C₁₀ olefins, Fischer-Tropsch ole¬ fins, dehydrogenated long chain paraffin hydrocarbons, thermally cracked hydrocar¬ bon waxes, or dimerized vinyl olefins and mixtures thereof;

(b) reacting via aminomethylation the internal olefin source with a primary amine or a secondary amine to produce a long chain internal fatty tertiary amines;

(c) optionally separating any unconverted hydrocarbons and color or odor bodies from the long chain fatty tertiary amines resulting in a purified long chain fatty tertiary amine product;

(d) optionally (with or without step (c)) oxidizing the long chain fatty tertiary amine to the corresponding amine oxide, and (e) optionally (with or without step (c) and/or (d)) quaternizing the long chain fatty tertiary amine into a quaternary long chain internal fatty tertiary amine product.

DETAILED DESCRIPTION OF THE INVENTION

As used herein "long chain internal olefin" means an olefin with 8 to 22 carbon atoms and greater than 10% of the carbon-carbon double bonds being in a position other than the terminal (α and/or β carbon) position on the olefin. Preferably more than 50%, 70%, 90% and up to 100% of the carbon-carbon double bonds are in a position other than the terminal (α and/or β carbon) positions on the olefin. The long chain internal olefin may be linear or branched. If the long chain internal olefin is branched, a C₁-C₅ carbon branch is preferred.

As used herein "internal amine" mean an amine having the amine moiety attached to the alkyl moiety in greater than 10%, 50%, 70%, 90% and up to 100% in a position other than the terminal (α and/or β carbon) position on the alkyl moiety.

Incorporated and included herein, as if expressly written herein, are all ranges of numbers when written in a "from X to Y" or "from about X to about Y" format. It should be understood that every limit given throughout this specification will include every lower or higher limit, as the case may be, as if such lower or higher limit was expressly written herein. Every range given throughout this specification will include every narrower range that falls within such broader range, as if such narrower ranges were all expressly written herein.

Without being limited by theory, it is believed that low cost production of long chain internal fatty tertiary amines is best accomplished by a process which uses low cost feedstocks, as manufacturing costs for a high volume, efficient chemical process are generally dominated by raw materials costs. Of the feedstocks available to produce long chain fatty tertiary amines, olefins are generally among the lowest cost materials. While alpha olefins are used to make terminal tertiary amines, long chain internal amines require a source of long chain internal olefins.

Long chain internal olefin sources can be obtained from a variety of different proc- esses, including C₂ to Ci _\ olefin oligomerization processes, C₅ to C₁Q olefin metathesis - A -

processes, Fischer-Tropsch processes, catalytic dehydrogenation of long chain paraf¬ fin hydrocarbons, thermal cracking of hydrocarbon waxes, and dimerized vinyl olefin processes.

The long chain internal olefins from any of the above described processes are then re¬ acted with primary or secondary amines to produce long chain fatty tertiary amines using commercially feasible processes such as aminomethylation. Any unconverted hydrocarbons and color or odor bodies are subsequently separated from the long chain internal fatty tertiary amines using distillation or other commercial techniques.

In the optional final step of the present process, the long chain internal fatty tertiary amines are converted into the corresponding amine oxide via oxidation.

The processes and methods herein may include a wide variety of other variations. The processes and methods of the present invention are described in detail hereinafter.

The present process relates to converting long chain internal olefins to long chain in¬ ternal fatty tertiary amines and optionally, long chain internal amine oxides.

Long Chain Internal Olefin Sources

Oligomerized C₂-C₁₁ Olefins

Long chain internal olefin sources from oligomerized C₂ to Cn olefins are readily available from a variety of sources, including natural gas, naptha, and gas oil frac- tions. Oligomerized ethylene is available from suppliers such as Shell Chemicals, Exxon Chemicals, BP Amoco and Chevron Phillips.

The oligomerized C₂ to C₁₁ olefins may be derived from C₂ to C₁₁ olefins in the pres¬ ence of either organoaluminum compounds, transition metal catalysts or acidic zeo- lites to produce a wide range of chainlengths that is further purified by various known means, preferably distillation (see US 3,647,906, 4,727,203, and 4,895,997 to Shell Oil Co., US 5,849,974 to Amoco Corp., and US 6,281,404 to Chevron Chemicals which disclose suitable catalysts and processing conditions for ethylene oligomeriza- tion). Oligomerization includes the production of dimers, trimers, or tetramers using cata¬ lysts such as acidic zeolites, nickel oxides, or metallocene cataylsts. For example, US 5,026,933 discloses the use of ZSM-23 zeolite for propylene oligomerization. Other suitable catalysts include AMBERLYST 36® and acidic zeolites including mordenite, offretite and H-ZSM- 12 in at least partially acidic form (see also Comprehensive Or¬ ganic Transformation, 2^nd Edition, Larock, Richard C, pages 633-636; and Vogel's Textbook of Practical Organic Chemistry, 5^th Edition, Furniss, Brian S., Hannaford, Antony J., Smith, Peter W.G., and Tatchell, Austin R., pages 574- 579).

Depending on the supplier and the process used, either α-olefins or internal olefins are generated from the oligomerization processes. For the case of α-olefϊn feedstocks or mixed α-olefϊn and internal olefin feedstock, an isomerization step is required to gen¬ erate the desired long chain internal olefins. The isomerization step results in random placement of the double bond along the carbon chain. Suitable isomerization catalysts include homogeneous or heterogeneous acidic catalysts, supported metal oxides such as cobalt oxide, iron oxide, or manganese oxide, and metal carbonyls such as cobalt carbonyl and iron carbonyl, see US 3,647,906, US 4,727,203, and US 4,895,997 to Shell Oil Co., US 5,849,974 to Amoco Corp., and US 6,281,404 to Chevron Chemi¬ cals which disclose suitable catalysts and processing conditions for double bond isom- erization.

Metathesis Of Cs-C₁₀ Olefins

Cross-metathesis of C₅-C₁₀ olefins with other olefins or even with oleochemicals can be used to produce suitable long chain internal olefins for the present process. For ex- ample, two octene molecules can be reacted to form tetradecene and ethylene. Or the methyl ester of oleic acid can be reacted with hexene to form dodecene and the methyl ester of lauric acid. Common homogeneous catalysts include the ruthenium based Grubb's catalyst as well as the Schrock catalyst. Cross metathesis is further described in the text Olefin Metathesis and Metathesis Polymerization by Mn and MoI (1997), and also the journal Chemical and Engineering News, vol. 80, no. 51, Dec 23, 2002, pp. 29-33.

Other Internal Olefins

Alternative processes for olefins are from the isomerization/disproportionation olefin process and/or SHOP® process from Shell Chemical. These are commercially avail¬ able materials under the tradename NEODENE®. Fischer-Tropsch Olefins and Paraffins

Long chain internal olefin sources from Fischer-Tropsch involves converting a source of carbon such as coal, methane, or natural gas to a wide distribution of carbon chainlengths and then isolating a narrow hydrocarbon fraction, using techniques such as distillation or liquid-liquid extraction.

Two different catalysts are commercially used: iron and cobalt, with iron generally producing a higher yield of olefins and cobalt producing a higher yield of paraffins. Hydrocarbons recovered from the Fischer-Tropsch reaction may be a mixture of linear and branched chains, olefins and paraffins, having both terminal and internal double bonds. Straight run Fischer-Tropsch olefin and paraffins from jet and/or diesel frac¬ tions may be utilized in the present process.

As disclosed above, double bond isomerization catalysts can be employed to convert α-olefϊns to internal olefins. Paraffins present in the internal olefin feed stream may be left with the internal olefins until amination is complete.

For the iron based Fischer-Tropsch reaction product, it may be desirable for oxygen¬ ates to be separated out from the hydrocarbons prior to amination. Oxygenates refer to carboxylic acids, alcohols, aldehydes, and ketones, which chainlengths from C₁ to C₁₈. Oxygenates impart undesirable color, odor, and performance impurities to tertiary amines and must be removed from the hydrocarbons prior to amination or from the crude tertiary amine after amination.

There are several methods to separate oxygenates from Fischer-Tropsch crude prior to amination. Liquid-liquid extraction is the preferred process for separating oxygenates from hydrocarbons. Liquid-liquid extraction is effective in removing both alcohols and carboxylic acids from hydrocarbons and can be achieved with more reasonable capital investment than distillation or adsorption. Caustic treatment, followed by cen- trifuging, water washing, or filtration is effective in neutralizing and separating car¬ boxylic acids, but has no effect on alcohols.

Use of liquid-liquid extraction to remove oxygenates can be done with a wide variety of solvents. For example, diethylene glycol is reported to be a solvent for removal of aromatics from reformate, and propane is reported to be a solvent for removal of fatty acids from natural oils. See Packed Tower Design and Applications, 2^nd Ed., Strigle, page 294. A wide variety of factors must be considered in the choice of the proper solvent, including solubilities, interfacial tension, differences between phase densities, viscosity, corrosion, and cost. Solvent polarity index is an important indicator of the solubility of the oxygenates as well as insolubility of the hydrocarbons. For a descrip- tion of polarity index see Practical HPLC Development, 2^nd Ed., Snyder, Kirkland, and Glajch, page 723; and Introduction to Modern Liquid Chromatography, 2^nd Ed., Snyder and Kirkland, pages 258-260. Applicants have found that it is preferred to use solvents with Fischer-Tropsch with a polarity index of 5.6 to 6.0. One suitable solvent is an 80/20 wt% mixture of ethanol/water. Temperature of operation for liquid extrac- tion is from 20° C to just below the boiling point of the solvent selected. Solvent to feed ratios of 0.1 to 3 are preferred.

Extraction can be carried out in three classes of equipment: mixer-settlers, contacting columns, or centrifugal contactors. When only one stage of separation is required for the extraction step, a mixer-settler may used. Spray columns may be used when the density difference between the phases is large. When more than three stages of separa¬ tion are needed, packed or tray columns with countercurrent flow are the preferred de¬ vices. Centrifugal contactors may also used if the liquid phases have small density dif¬ ference and a large number of equilibrium stages are needed. When ten to twelve equi- librium stages are required, a mechanical contactor with rotating disks or impellers is often used, as these have higher efficiencies than the packed contactors. The preferred number of equilibrium stages is one to twelve.

In theory, distillation can be used to separate oxygenates from hydrocarbons, but the boiling points of oxygenates and hydrocarbons can overlap so that distillation is not preferred. Bulk separation by adsorption using molecular sieves is also possible, but expensive from a capital investment standpoint.

Dehydrogenation of Long Chain Hydrocarbons Long chain internal olefin sources may also be obtained from the catalytic dehydroge¬ nation of long chain paraffins or paraffϊn/olefm mixtures which yields long chain ole¬ fins with the same number of carbon atoms and with random locations of a double bond along the chain. As disclosed above, double bond isomerization catalysts can be employed to convert α-olefins to internal olefins. Paraffins present in the internal ole- fin feed stream may be left with the internal olefins until amination is complete. Sources include the kerosene fraction from petroleum refineries and Fischer-Tropsch paraffins or paraffin/olefin mixtures. See US 3,531,543 to Chevron Research and US 3,745,112, US 3,909,451, and 4,608,360 to UOP which discuss suitable catalysts and processing conditions for paraffin dehydrogenation. Straight run Fischer-Tropsch ole¬ fin and paraffins from jet and/or diesel fractions may be utilized in the catalytic dehy¬ drogenation process. The UOP PACOL® process operates at 450° C to 510° C and 0.3 MPa using a platinum on alumina catalyst, promoted by lithium, arsenic, or germa¬ nium. To minimize by-products, low conversion rates of 10 to 15 wt % are used. Use of the low conversion rate results in paraffin-olefin mixtures that may be further sepa¬ rated and purified by the UOP OLEX® process or reacted together with amine before paraffin separation is done.

Thermally Cracked Hydrocarbon Waxes Long chain internal olefins may also be derived from thermal cracking of hydrocarbon waxes from either petroleum streams or the Fischer Tropsch reactions, including Fischer Tropsch paraffin waxes. The chainlength of these waxes is generally greater than C₂₂. Thermal cracking is a non-catalytic, free radical process conducted at high temperatures in the presence of steam, followed by distillation to separate and recycle the unreacted wax to the cracking furnace.

A tubular furnace is preferably used for the cracking reaction. The temperature for the thermal cracking ranges from 400 to 600°C. Selection of higher temperatures are not desired as higher temperatures results in the formation of shorter chain olefins (chainlength < C₅), higher levels of polyolefϊns, as well as more gas products. Selec¬ tion of lower temperatures are not desired as lower temperatures reduce the conver¬ sion of long chain internal olefins per pass, which is undesirable from a capital cost standpoint.

The pressure in the thermal cracking reaction zone is 0.1 to 1 MPa. Higher pressure generally leads to an increase in the yield of liquid products, with a corresponding re¬ duction in α-olefin content. Space velocity is 1.25 to 5.0 volume of feed/volume of reactor/hour. This corresponds approximately to a vapor residence time in the reactor of 2.5 to 10 seconds. Higher residence time is undesirable as it leads to increased de- composition and secondary by-products verses the desired long chain internal olefins. The conversion per pass in the reaction is 10 to 25 wt %. Gas and liquid products from the thermal cracking reactor are separated by a distilla¬ tion step using a pressure of 10 to 2500 Pa and a temperature of 100° C- 280° C. Any unreacted wax is taken as a bottom fraction from the distillation step and recycled back to the thermal cracking furnace and mixed with fresh hydrocarbon waxes. As disclosed above, double bond isomerization catalysts may be employed to convert any α-olefins present to long chain internal olefins.

Internal Vinylidenes

Internal vinylidenes may also be utilized as the long chain internal olefin source of the present process. Vinylidenes may be produced via a process involving dimerizing vi¬ nyl olefin with at least one trialkylaluminum compound. Further conditions may be found in US 5,625,105. Vinylidenes may also be produced via a process of dimerizing a vinyl-olefin monomer in the presence of a tri-alkyl aluminum catalyst as described in US 4,973,788.

Reaction Of Long Chain Internal Olefins With Primary Or Secondary Amines Using Aminomethylation Conditions:

The long chain fatty tertiary amines desired in the present process are produced by the reaction between the long chain internal olefins as described above and either a pri¬ mary or secondary alkyl amine. If a primary alkyl amine such as monomethylamine is used, then two long chain internal olefin molecules are added to the primary alkyl amine to produce a di-long chain fatty tertiary monoalkyl amine product. If a secon¬ dary alkyl amine such as dimethylamine is used, then one long chain internal olefin molecule is added to the secondary alkyl amine to produce a mono-long chain fatty tertiary dialkyl amine product.

Tertiary amine products that are produced by the process of the present invention have an internal amine content of from 10 wt% to 100 wt%, a linear olefin content of from about 1 wt% to 100 wt%, and a paraffin content of from 0 wt% to about 90 wt%.

Examples of desirable tertiary amine products include but are not limited to trioc- tylamine, tridecylamine, tridodecylamine, didodecylmethylamine, ditetradecylmethyl- amine, dihexadecylmethylamine, dioctadecylmethylamine, decyldimethylamine, do- decyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, and octade- cyldimethylamine. The amine moiety of these materials is located on the long chain alkyl in an internal position. An internal position refers to a carbon other than the α or β carbon of the long chain alkyl. Aminating the internal olefins for the present process includes hydrocarbonylation and is further described below.

In one embodiment of the present process, the aminomethylation reaction with an in- ternal long chain olefin such as those feedstocks described above produces a tertiary amine with the following structure:

wherein R₁ and R₂ are linear or semilinear hydrocarbons with a hydrocarbon content of chainlength of 1 to 19 carbon atoms. As used herein "semi-linear" means that R₁ and/or R₂ comprise between 1 and 4 C₁ to C₃ alkyl branches randomly distributed or consistently distributed. The amine structure is such that an alkyl portion has a total sum of carbons from 8 to 22 carbon atoms. As used herein, the alkyl portion is R₁ + R₂ + 2 carbon atoms between the nitrogen and R₁ and R₂ in the above referenced structure.

In a preferred embodiment, the total sum of carbons in the alkyl portion (R₁ + R₂ + 2 carbons) is from 10 to 22 carbon atoms, preferably from 12 to 20, more preferably from 10 to 14. The number of carbon atoms for R₁ may be approximately the same number of carbon atoms for R₂ such that R₁ and R₂ are symmetric. As used herein "symmetric" means that for carbon atoms, | R₁ - R₂ | is less than or equal to 5 carbon atoms in at least 50 wt%, more preferably at least 75 wt% to 100 wt% of the long chain fatty internal amine produced herein. In another embodiment | R₁ — R₂ | is less than 4.

Without being limited by a theory, it is believed that the symmetric structure of the long chain fatty internal amine oxides improve surface wetting ability of the amine oxide that aids in the removal of grease deposits from surfaces at lower wash tempera¬ ture verses asymmetric branched amine oxides. As used herein "asymmetric" means | R₁ - R₂ I is greater than 5 carbon atoms. However, mixtures contain non symmetric and symmetric structures of the long chain fatty internal amine oxides may also be de- sirable for the purpose but are not preferred. According to a preferred embodiment of the present invention the process comprises the step of reacting the olefins with synthesis gas (H₂ and CO), preferably in a stoichiometric ratio, and a primary or secondary amine in the presence of a catalyst, preferably a heterogeneous catalyst, to form a tertiary amine product. Preferred proc¬ ess conditions are a temperature of 60 to 200° C pressure of 2.8 to 21 MPa (400 to 3000 psig), H₂:CO molar ratio of 0.5 to 3.0, and reaction time of 0.1 to 10.0 hours. The catalyst suitable for use in the present process include noble metal catalysts such as rhodium oxide, rhodium chloride, or ruthenium chloride, at a catalyst level of 50 to 1000 ppm by weight of the olefin. Ligands such as triphenylphosphine may optionally be used to stabilize the preferably heterogeneous noble metal catalyst. Preferred levels of triphenylphosphine are 100 to 5000 ppm by weight of the olefin.

Optional Purification of the internal fatty tertiary amines using thermal separation techniques

The process of the present invention further comprises the step of purifying the long chain internal fatty tertiary amine product from the previous step to form a purified long chain internal fatty tertiary amine product. Preferred purity of the purified long chain internal fatty tertiary amine product is from about 95 wt% or greater, more pref¬ erably from about 97 wt% or greater, most preferably from about 98 wt% to about 100 wt% by weight of the purified long chain internal fatty tertiary amine product after the purification step.

The long chain internal fatty tertiary amine products may be mixed with paraffins, un- reacted olefins, color and odor bodies, and small quantities of oxygenates such as al¬ cohols or carboxylic acids among other impurities.

Each of the impurities listed above may be removed via thermal separation tech- niques. A preferred purification step is via flash stills and/or topping columns. Equip¬ ment for the flash still and the topping column includes falling film evaporators, wiped film evaporators, reboiler flash units, and multistage distillation columns. All equipment is known to one of skill in the art and available from suppliers such as Pfaudler, Lewa, and Koch. Heavy impurities such as polyalkylamines, salts, and color bodies may be removed in a bottom stream of a flash still operating under a pressure of 10 to 2500 Pa (0.1 to 20 mm Hg) and a temperature of 90 to 205° C. Light impuri¬ ties such as residual hydrocarbons (olefin or paraffin) and color bodies may be re¬ moved in the overheads stream of a topping column operating under a pressure of 10 to 2500 Pa (0.1 to 20 mm Hg) and a temperature of 150 to 250° C.

Optional Oxidation Step Of The Purified Internal Fatty Tertiary Amines The process of the present invention further comprises the optional step of oxidizing the purified long chain internal fatty tertiary amine to give an oxidation product of the corresponding long chain internal fatty amine oxide. The purified long chain internal fatty tertiary amine may optionally be converted into using materials such as 5-70 wt% hydrogen peroxide. As described in US 6,294,514 to Procter & Gamble Co., pu¬ rified long chain internal fatty tertiary amines are typically combined with 5 to 70 wt% hydrogen peroxide, 0.3 to 2.5% of a bicarbonate material such as sodium bicar¬ bonate or potassium bicarbonate, and optionally water, to result in an oxidation prod- uct which is 30-38 wt% by weight of the oxidation product of the corresponding long chain internal fatty amine. The amount of hydrogen peroxide is 100 to 115% of stoichiometric to the amount of amine present. The oxidation step target temperature is about 40 to 100° C (60 to 70° C preferred), and pressure is 0.1 MPa.

The oxidation step is complete when the residual hydrogen peroxide level is below 1%, preferably below 0.1 wt% of the final product composition. Reaction time is gen¬ erally 4 to 24 hours. Residual hydrogen peroxide is typically decomposed by holding the material at reaction temperature. If necessary, 0.1 to 5 wt% by weight of the re¬ agents of platinum on alumina may be used as an adsorbent to remove residual hydro- gen peroxide from the oxidation product.

Optional Quaternization Step of the Purified Internal Fatty Tertiary Amines

The process of the present invention may further comprise the optional step of quater- nizing the purified long chain internal fatty tertiary amine to give a quaternary long chain internal fatty tertiary amine product. Quaternization may be achieved by a reac¬ tion of the purified long chain internal fatty tertiary amine with methyl chloride or di¬ methyl sulfate. Quaternization with methyl chloride is achieved by reaction with 1.0 to 1.3 mole equivalents of methyl chloride relative to the purified long chain internal fatty tertiary amine in an autoclave with temperature range of room temperature (20⁰C) to 8O⁰C under nitrogen pressure from 101 to 10100 kPa (1 to 100 atm). Dimethyl sulfate is reacted at 1.0 to 1.1 mole equivalents relative to the purified long chain internal fatty tertiary amine in a flask blanketed with nitrogen at 10 to 7O⁰C to form the desired quaternary long chain internal fatty tertiary amine product.

Examples

The following examples further describe and demonstrate embodiments within the scope of the present invention. These examples are given solely for the purpose of il¬ lustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the invention.

Example 1 - Thermal Cracking Of Paraffin Wax, Isomerization, And Aminomethyla- tion

Step 1 Melt a paraffin wax with a melt point range of 52 to 58° C and a linear hydrocarbon chainlength of C₂₁ to C₃₆ in an 800 niL glass beaker. Use the following equipment for the thermal cracking reaction:

FMI piston pump (model QSY-I) to meter melted paraffin wax into a tubular reactor - 3.35 m (11 foot) long by 4.57 mm (0.18 inch) diameter stainless steel coil, heated in a muffle furnace (preheater)

3.66 m (12 foot) long by 4.57 mm (0.18 inch) diameter coil, placed inside a second muffle furnace (reactor)

9.14 m (30 foot) long by 4.57 mm (0.18 inch) diameter coil, placed inside a 2 liter beaker filled with water (quench cooler)

1 liter beaker for containing a quenched liquid product

Stainless steel tubing, electric traced, with thermocouples before & after reac¬ tor coil

Crack the melted paraffin wax using a mass flowrate of 2.6 g/min. with a residence time of 3.4 volumes liquid feed/volume of reactor/hour, and a reactor temperature of 575° C. Meter 652 grams of melted paraffin wax into the tubular reactor and recover a product comprising about 579 grams of liquid product with the balance of the product of non-condensable vapor and gas. Collect the product from the reactor, the product includes cracked olefins as well as unreacted paraffins. Separate the olefins from the unreacted paraffins in a flash still at 667 Pa (5 mm Hg) and a temperature of 200 °C, then analyze using a Hewlett Packard 6890 Series gas chromatograph. About 67 grams of distillate may be recovered.

The distillate composition was as follows:

Ci₀-C₂₀ α-olefin 93.1 wt%

C₁₀-C₂₀ di-olefm 2.5 wt%

C₁₀-C₂₀ paraffin 2.8 wt%

Ci_O-C₂₀ other 1.6 wt% internal olefin 0 wt% branched olefin 0 wt% aromatics 0 wt%

The carbonyl value (expressed as C=O) is 32 ppm, indicating minimal oxidation of the hydrocarbons.

Step 2 Place 50 grams of Ci₀ to C₂₀ distillate composition from Step 1 above in a 300 ml Parr autoclave and combine with 0.025 grams of iron carbonyl, Fe₂(CO)₉ to isomerize any double bonds present to result in internal olefins. Purge the reactor with 349.35 kPa (50 psig) nitrogen gas and then heat the distillate composition and iron carbonyl to 180° C for one hour with agitation.

Cool the reactor to 40° C and add 0.052 grams of rhodium oxide with 0.131 grams of triphenylphosphine ligand. Purge the reactor ten times with 349.35 kPa (50 psig) ni¬ trogen gas, then purge twice with 3493.5 kPa (500 psig) synthetic gas (syngas). Add 13.5 grams of dimethylamine to the reactor. Pressurize the reactor to 7685.7 kPa (1100 psig) with syngas using a 0.5 molar ratio of H₂:CO. Conduct the reaction for 3 hours at 150° C, and then cool to 40° C and depressurize the reactor to result in a crude product. GC-MS analysis should indicate a majority of the crude product from the reactor was linear and branched monoalkyldimethyl amine.

Example 2 - Isomerization of α-olefms, followed by aminomethylation and oxidation. Step 1

Add 18.6 kg (41 pounds) of Cio α-olefin and 7.71 kg (17 pounds) of Cj₂ α-olefin to a 75.7 L (20 gallon) agitated reactor along with 25 grams iron carbonyl as an isomeriza- tion catalyst. Pressurize the reactor to 139.74 kPa (20 psig) with nitrogen gas, then heat the reactor to 180° C for one hour to allow double bond isomerization to take place.

Alternative Step 1 :

Add from a container a mixture of 15.1 g of NEODENE® 10, 136.6 g of NEODENE® 12 and 109.1 g of 1-tridecene to a 7.57 L (2 gallon) stainless steel, stirred autoclave along with 70 g of a shape selective catalyst (acidic beta zeolite catalyst ZEOCAT ^M PB/H). NEODENE® 10 and 12 are commercially available olefins from the Shell Chemical Company. Wash the residual olefin and catalyst in the container into the autoclave with 200 mL of n-hexane and seal the autoclave. Purge the autoclave twice with 1724.25 kPa (250 psig) nitrogen gas, and then charged to 413.82 kPa (60 psig) nitrogen gas. Stir and heat the mixture to 170⁰C to 175°C for about 18 hours then cool to 70°C-80°C. Open the valve leading from the autoclave to a benzene condenser and collection tank. Heat the autoclave to about 60⁰C then continue to heat to 12O⁰C with continuous collection of hexane in collection tank. No more hexane should be col- lected by the time the reactor reaches 120⁰C. Cool the reactor to 4O⁰C and pump with mixing 1 kg of n-hexane into the autoclave. Drain the autoclave to remove the reac¬ tion mixture product. Filter the reaction mixture product to remove catalyst and evaporate the n-hexane under low vacuum. Distill the reaction mixture product under high vacuum (133 Pa - 667 Pa [1-5 mm of Hg]) to give an internal olefin mixture. Collect about 21O g of the internal olefin mixture at a temperature of 85°C - 15O⁰C.

Cool the reactor to 50° C, depressurize the reactor, and then add the following ingre¬ dients to the reactor: 26 grams rhodium oxide, 65 grams triphenylphosphine, and 7.71 kg (17.6 pounds) of dimethylamine. Pressurize the reactor to 6987 kPa (1000 psig) with syngas (the syngas having a COrH₂ molar ratio of 1:1) and then heat to 150° C for three hours resulting in a mixed product having a unreacted dimethlamine phase and a tertiary amine phase. A GC analysis indicated that the mixed product was 61 wt% tertiary amine and 39 wt% unreacted olefin. Cool the reactor and pour the mixed product into 18.0 L (5 gallon) plastic buckets. Settle any unreacted dimethylamine (DMA) phase into a separate phase and decant the tertiary amine phase off the top to give a crude tertiary amine product. Use batch distillation to remove DMA and any unreacted olefin from the tertiary amine crude product in a 7.62 cm (3 inch) glass batch still with 7 stages of separation and reflux. Add 31.1 kg (68.5 pounds) of the crude tertiary amine to a stillpot and dis- till under vacuum using the following conditions:

Beginning of Distillation End of Distillation

Top pressure 1.51 kPa (11.3 mm Hg) 1.15 kPa (8.6 mm Hg)

Bottom pressure 1.96 kPa (14.7 mm Hg) 1.83 kPa (13.7 mm Hg)

Top temperature 60° C 132° C Bottom temperature 85° C 144° C

As used herein "reflux ratio" is defined as the mass flow of distillate sent back to col¬ umn divided by mass flow of distillate removed from the column. The reflux ratio may be varied from 1.0 to 4.0. Recover a number of distillate fractions with various levels of unreacted olefin and unreacted amine. Cease column boilup and stop the dis¬ tillation and cool. Recover about 2.13 (4.7 pounds) of still bottoms.

Combine the distillate fractions with the highest purity of tertiary amine in a blend with greater than 99 wt% C₁₁ and C₁₃ amines and less than 1 wt% C_1O and C₁₂ olefins. Use a lab distillation to recover pure C₁₁ amine using a 5.08 mm (2 inch) glass Older- shaw column with 10 trays. As used here, "pure C₁₁ amine" means that the weight percent of C₁₁ amine is greater than 99 wt%. Add 2230 grams of the distillate to the stillpot and distill under vacuum using the following conditions:

Beginning of Distillation End of Distillation

Top pressure 667 Pa (5 mm Hg) 800 Pa (6 mm Hg)

Bottom pressure N/A N/A

Top temperature 82° C 88° C Bottom temperature 125° C 131° C

Set the reflux ratio at 6.0 throughout the distillation. Stop the distillation after several distillate fractions are collected with C₁₁ tertiary amine present. Collect about 600 grams of distillate and leave about 1630 grams of still bottoms in the stillpot. An oxidation step may be done in a 3 liter agitated flask. Add 600 grams of C]₁ terti¬ ary amine, 506 grams of 50 wt% hydrogen peroxide, 1049 grams of water, and 0.44 grams of DEQUEST® 2066 chelant to a glass flask and heat to 65° C with agitation. After 10 hours of mixing, the composition of the mix should result in about 1.1 wt% residual peroxide, 2.1 wt% petroleum ether extract, no detectible free amine, and 28 wt% active amine oxide.

Adsorb the residual peroxide with an adsorbent of a 0.5% platinum on alumina over five successive batch additions and fϊltrations using a Buchner funnel with filter pa- per. Treat a total of about 2150 grams of amine oxide with a total of 32 grams of the adsorbent. The final product should result in about 0.09 wt% residual peroxide, 2.1 wt% petroleum ether extract, no detectible free amine, and 28 wt% active amine ox¬ ide. Color measured using a spectrophotometer with a 1 mm cell referenced to water results in a % transmittance of 96.4% at 470 nm.

Example 3 - Metathesis of α-olefins, followed by aminomethylation.

Step 1

6-Dodecene was prepared via metathesis of 1-heptene using Grubbs Catalyst [1^st gen- eration, benzylidene-bis(tricyclohexylphosphine)dichlororuthenium]. The 6-dodecene was purified from the reaction mixture using fractional vacuum distillation.

Step 2

The 6-dodecene produced in Step 1 was aminomethylated using the following experi- mental procedure:

Rh₂O₃ (0 .525mM) 10.25 mg

TPP (P :Rh = 1.2: 1) 26 mg

6-Dodecene 13 ml

Me₂NH 3.0 g

Rh₂O₃, TPP and the olefin were heated under nitrogen (~1 bar) to 150⁰C. Me₂NH was injected using syngas (H₂:CO 2:1) 76bar and syngas was fed at this pressure for 2Oh. GC and GCMS analysis showed the following product distribution: olefm conversion 90% aldehydes 17.2% enamines 11.4% alcohols 8.3% amines 63%

The amine product distribution was as follows: a 2-Pentyloctyldimethylamine 32.7% b 2-Butylnonyldimethylamine 27.3% c 2-Propyldecyldimethylamine 12.2% d 2-Ethylundecyldimethylamine 9.5% e 2-Methyldodecyldimethylamine 13.6% f Linear-tridecyldimethylamine 4.8

Example 4 - Dehydrogenation of long chain paraffin hydrocarbons, followed by ami- nomethylation.

A commercially available Cj₁C₁₂ olefin feed derived from Pacol dehydrogenation of a C₁₁C₁₂ paraffin mixture (olefin composition C_{1 \} - 44.5%, C₁₂ ~ 55.5%) was converted to amines using the following experimental procedure:

Rh₂O₃ (0.525mM) 10.2 mg

TPP (P:Rh = 1.2:1) 26 mg

C₁₁C₁₂ Pacol olefins 13 ml Me₂NH 3.43 g

Rh₂O₃, TPP and the olefin were heated under nitrogen (~1 bar) to 15O⁰C. Me₂NH was injected using syngas (H₂: CO 2:1) 76bar and syngas was fed at this pressure for 2Oh. GC analysis showed: (small amounts of products from ClO & C13 olefins as well as aromatics in the feed were ignored at this stage).

conversion 82% alcohols ~5% aldehydes -38.5% enamines -21.4% amines -35.1% The amine distribution was as follows:

C13 amines from C12-olefins a 2-Pentyloctyldimethylamine 13.2% b 2-Butylnonyldimethylamine 16.6% c 2-Propyldecyldimethylamine 2.5% d 2-Ethylundecyldimethylamine 3.0% e 2-Methyldodecyldimethylamine 5.3% f Linear-tridecyldimethylamine 7.4%

Cl 2 amines from CIl -olefins g 2-Pentylheptyldimethylamine 1.2% h 2-Butyloctyldimethylamine 2.3% i 2-Propylnonyldimethylamine 9.5% j 2-Ethyldecyldimethylamine 17.6% k 2-Methylundecyldimethylamine 13.1%

1 Linear-dodecyldimethylamine 8.3%

Example 5 - Dimerisation of α-olefins to vinylidene olefins, followed by ami- nomethylation.

Step 1

1-Hexene was dimerized using zirconocene dichloride (Cp₂ZrCl₂) and methylalumox- ane (Al:Zr:olefϊn 50:1 :1000) and purified via fractional vacuum distillation. The major product was 2-butyl-l-octene (C12-vinylidene).

The hydro aminomethylation of 2-butyl-l-octene (C12-vinylidene) was done using the following experimental procedure:

Rh₂O₃ (0 .525mM) 10.2mg

TPP (P :Rh = 1.2: 1) 26mg

2-Butyl-l-octene 13ml

Me₂NH 3.38g Rh₂O₃, TPP and the olefin were heated under nitrogen (~1 bar) to 15O⁰C. Me₂NH was injected using syngas (H₂)CO 2:1) 76bar and syngas was fed at this pressure for 2Oh.

3-Butylnonyldimethylamine

GC analysis indicated: conversion 83% paraffins 5% enamines 38% aldehydes 18% amines 39%.

The amine distribution was >97% to the required 3-butylnonyldimethylamine isomer.

All documents cited in the Detailed Description of the Invention are, are, in relevant part, incorporated herein by reference; the citation of any document is not to be con¬ strued as an admission that it is prior art with respect to the present invention.

While particular embodiments of the present invention have been illustrated and de¬ scribed, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the inven¬ tion. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this inventio

Claims

1. A process comprising the steps of: a) providing a long chain internal olefin source; b) reacting via aminomethylation the internal olefin source with a primary amine or a secondary amine to produce fatty tertiary amines; c) optionally separating any unconverted hydrocarbons optionally including color or odor bodies from the long chain fatty tertiary amines resulting in a purified long chain fatty tertiary amine product.

2. The process of Claim 1 wherein the process further comprises the step of: d) converting the purified long chain fatty tertiary amine product into a long chain fatty amine oxide product.

3. The process of Claim 1 wherein the process further comprises the step of: e) quaternizing the long chain fatty tertiary amine into a quaternary long chain internal fatty tertiary amine product.

4. The process according to at least one of the preceding Claims wherein the long chain internal olefin source is selected from the group consisting of oligomerized C₂ to Cn olefins, methathesized C₅ to C₁₀ olefins, Fischer-Tropsch olefins and paraffins, dehydrogenated long chain paraffin hydrocarbons, thermally cracked hydrocarbon waxes, or dimerized vinyl olefin and mixtures thereof.

5 The process according to at least one of the preceding Claims wherein the long chain internal olefin source is selected from oligomerized C₂ to C₁₁ olefins wherein the oligomerized C₂ to C₁₁ olefins are obtained from an oligomerization step utilizing an organoaluminum compound, a transition metal catalyst, an acidic zeolite, nickel oxides or a metallocene catalyst to produce the long chain internal olefin source.

6. The process according to at least one of the preceding Claims wherein the long chain internal olefin source results from an isomerizing step that converts a α-olefin feedstock or a mixed α-olefin and internal olefin feedstock utilizing an acidic catalyst, a metal oxide, or a metal carbonyl catalyst.

7. The process according to at least one of the preceding Claims wherein the long chain internal olefin source is selected from Fischer Tropsch olefins, paraffin and mix¬ tures thereof.

8. The process according to at least one of the preceding Claims wherein the long chain internal olefin source results from an isomerizing step that converts a α-olefin feedstock or a mixed α-olefin and internal olefin feedstock utilizing an acidic catalyst, a metal oxide, or a metal carbonyl catalyst.

9. The process according to at least one of the preceding Claims wherein before step (b), the process further comprises the step of removing C₁ to C₁₈ oxygenates via liquid-liquid extraction, caustic treatment, distillation, molecular sieves, or mixtures thereof.

10. The process of Claim 9 wherein the removing step is selected as liquid- liquid extraction via the use of a solvent having a polarity index of 5.6 to 6.0.

11. The process of Claim 10 wherein the removing step is carried out at a tempera- ture from about 20°C to a temperature just below the boiling point of the solvent se¬ lected; wherein the solvent to long chain internal olefin source ratio is from 0.1 to 3.

12. The process of Claim 9 wherein the oxygenates are selected from carboxylic acids, alcohols, aldehydes, ketones and mixtures thereof.

13. The process of Claim 10 wherein the removing step utilizes mixer-settlers, contacting columns, or centrifugal contactors.

14. The process according to at least one of the Claims 9 to 13 wherein in the re- moving step comprises from 1 to 12 equilibrium stages.

15. The process of Claim 14 wherein the removing step comprises 10 to 12 equi¬ librium stages and contacting columns are utilized; wherein the contacting columns are packed or tray columns with countercurrent flow.

16. The process according to at least one of the preceding Claims wherein the long chain internal olefin source is selected from dehydrogenated long chain paraffins or long chain paraffin/olefϊn mixtures.

17. The process according to at least one of Claims 1 to 15 wherein the long chain internal olefin source is selected from thermal cracked hydrocarbon waxes from petro¬ leum streams or Fischer-Tropsch reactions wherein the long chain internal olefin source is produced from the step of heating the hydrocarbon waxes in a tubular fur- nace from 400 to 600°C; 0.1 to 1 MPa; a space velocity of from 1.25 to about 5.0 vol¬ ume of feed/volume of reactor/hour; and a conversion per pass in the reaction is 10 to 25 wt %.

18. The process according to at least one of Claims 1 to 15 wherein the long chain internal olefin source comprises α-olefins that are converted to the corresponding long chain internal olefins by isomerizing the α-olefms in the presence of an isomerization catalyst.

19. The process according to at least one of Claims 1 to 15 wherein the long chain in- ternal olefin source is selected from internal vinylidene produced by dimerizing vinyl olefin.

20. The process according to at least one of the preceding Claims wherein step (b) comprises the use of a primary alkyl amine such that for every one molecule of pri- mary alkyl amine, two molecules of a long chain internal olefin from the long chain internal olefin source is added to produce a di-long chain fatty tertiary amine product.

21. The process according to at least one of Claims 1 to 19 wherein step (b) com¬ prises the use of a secondary alkyl amine such that for every one molecule of secon- dary alkyl amine, one molecule of a long chain internal olefin from the long chain in¬ ternal olefin source is added to produce a mono-long chain fatty tertiary amine prod¬ uct.

22. The process according to at least one of the preceding Claims wherein the long chain fatty tertiary amine product comprise a paraffin content of from 0 wt% to about

90 wt% by weight of the long chain fatty tertiary amine product.

23. The process according to at least one of the preceding Claims wherein the long chain fatty tertiary amine product is selected from the group consisting of trioc- tylamine, tridecylamine, tridodecylamine, didodecylmethylamine, ditetradecylmethyl- amine, dihexadecylmethylamine, dioctadecylmethylamine, decyldimethylamine, do- decyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, octade- cyldimethylamine, and mixtures thereof.

24. The process according to at least one of the Claims 1 to 22 wherein the long chain fatty tertiary amines comprises the following structure:

wherein R₁ and R₂ are linear or semi-linear hydrocarbons with a chain length of 1 to 19 carbon atoms.

25. The process according to at least one of the preceding Claims wherein in step (b) the process comprises the step of reacting the olefins with synthesis gas in the presence of a primary or secondary amine and a catalyst, preferably a heterogeneous catalyst.

26. The process according to at least one of the preceding Claims wherein step (b) is conducted at a temperature of 60 to 200° C; pressure of 2.8 to 21 MPa, H₂:CO mo- lar ratio of 0.5 to 3.0, and reaction time of 0.1-10 hours.

27. The process according to Claim 25 or 26 wherein the catalyst consists of rho¬ dium oxide, rhodium chloride, or ruthenium chloride at a level of 50 to 1000 ppm by weight of the olefin.

28. The process of Claim 25, 26 or 27 wherein triphenylphosphine or an substi¬ tuted triarylphosphine is added to stabilize the catalyst at a level of 100 to 5000 ppm by weight of the olefin.

29. The process according to at least one of the preceding Claims wherein the puri¬ fied long chain fatty amine product of step (c) comprises from about 95 wt% to about 100% by weight of the purified tertiary amine product of a long chain fatty amine.

30. The process according to at least one of the Claims 2 to 29 wherein step (d) comprises mixing hydrogen peroxide, water and the purified long chain fatty amine product to produce a long chain internal amine oxide product.

31. The process according to at least one of the Claims 2 to 29 wherein step (d) has a temperature of about 40-100°C and a pressure of about 0.1 MPa.

32. The process according to at least one of the Claims 2 to 29 wherein step (d) is continued until the hydrogen peroxide is less than 1 wt% of the original level of hy¬ drogen peroxide added.

33. The process according to at least one of the Claims 2 to 29 wherein step (d) is continued until the hydrogen peroxide is less than 0.1 wt% of the original level of hy- drogen peroxide added.

34. The process according to at least one of the Claims 2 to 29 wherein step (d) further comprises 5 wt% by weight of the reagents of platinum on alumina.