CN104232323B - The preparation process of fatty acid isooctyl - Google Patents

Abstract

The present invention relates to the preparation process of fatty acid isooctyl, including aliphatic acid and isooctanol is made to react in the presence of a catalyst, wherein the catalyst is selected from bisulfate, support type bisulfate, support type p-methyl benzenesulfonic acid and combination thereof.Present invention process at least has one of the following advantages：Reaction conversion ratio is high, isooctanol and catalyst amount are low, reaction condition is mild, do not generate or seldom generate side reaction, aftertreatment technology is simple and environmental-friendly.

Description

The preparation process of fatty acid isooctyl

Technical field

The present invention relates to the preparation process of fatty acid isooctyl, more particularly to 16 carbon saturated fatty acids and/or 18 Carbon saturated fatty acid is the preparation process of the different monooctyl ester of the aliphatic acid of key component.

Background technology

The different monooctyl ester of 16-18 carbon saturated fatty acids（Hereinafter referred to as fatty acid isooctyl）, in tasteless transparence liquid, it is not easy Oxidation, non-discolouring, stability is good, there is good moisturizing, antiperspirant and permeability, is a kind of nontoxic, nonirritant, anti-without anaphylaxis The nonionic surfactant answered, is widely used in daily chemical product.At present, the fatty acid isooctyl is in daily use chemicals and plastic processing Etc. demand is very big in industries, and increased severely with annual 10% or so speed, and domestic existing production capacity cannot meet market need It asks, largely relies on import.Therefore, it is necessary to strengthen the research in terms of fatty acid isooctyl synthesis.

Fatty acid isooctyl is typically to be made with palmitic acid and/or stearic acid with isooctanol through catalytic esterification, wherein different pungent Alcohol typically refers to 2- ethyl-hexanols, and reaction equation is as follows：

。

Fatty acid isooctyl is prepared, traditional handicraft is mostly using the concentrated sulfuric acid, p-methyl benzenesulfonic acid, trichloroacetic acid etc. as catalysis Agent, and add water entrainer, after reaction with alkali neutralization, through washing, being layered, the techniques such as being evaporated under reduced pressure and obtain product, referring to Zhao Know beautiful etc., " synthesis progress of isobutyl palmitate ", Liaoming Petrochemical Univ's journal, 2006,26（04）, 62-66；And Tang Pattern etc., " synthesising process research of isobutyl palmitate ", chemical intermediate, 10 phases in 2007（The content of these documents is drawn through this With being incorporated herein）.The shortcomings that technique is that by-product is more, serious corrosion of equipment；Reaction process with water entrainer or negative pressure band water, instead Should terminate need to be through post processings such as alkali neutralization, washings, thus complex process and generate a large amount of waste water, and product color is deep.

Chinese patent application discloses CN101747187A（It is incorporated herein by this reference）In to disclose a kind of palmitic acid different The preparation method of monooctyl ester, is included in nitrogen atmosphere, makes palmitic acid and isooctanol in the presence of solid acid catalyst, in 100- Water entrainer is added in water knockout drum when 180 DEG C of reaction 2-6 are small, in reaction process and carry out band water, wherein solid catalyst used is grass Sour stannous, SO₄ ^2-/ZrO₂-Al₂O₃Or SO₄ ^2-/TiO₂-SnO₂-Al₂O₃.It the method overcome equipment during using the concentrated sulfuric acid as catalyst Seriously corroded, catalyst are not readily separated, post-process complexity and lead to the problem of a large amount of waste water.But there are isooctanol for this method The problem of dosage and larger catalyst amount, such as in the method when molar ratio of alcohol to acid is 1：When 2, the receipts of isobutyl palmitate Rate is only 85.5%；And catalyst amount be 2% when, the yield of isobutyl palmitate is only 93.5%.

Afterwards, scholar has studied microwave assisting method and enzyme catalysis method, wherein microwave assisting method is not easy to industrialize, and enzyme is urged Although change method by-product is few, without heavy corrosion, the reaction time is long, and enzyme easy in inactivation.

Therefore, a kind of high conversion is sought, isooctanol and catalyst amount are low, post-process simple and environmental-friendly fat The different monooctyl ester synthesis technology of acid, is of great significance to the production and supply of fatty acid isooctyl.

The content of the invention

For many deficiencies of existing fatty acid isooctyl preparation process, the present invention is intended to provide a kind of new aliphatic acid Different monooctyl ester synthesis technology, the technique at least have one of the following advantages：Reaction conversion ratio is high, isooctanol and catalyst amount are low, Reaction condition is mild, do not generate or seldom generate side reaction, aftertreatment technology is simple and environmental-friendly.

Therefore, in one aspect, the present invention provides the preparation process of fatty acid isooctyl, including making aliphatic acid and different pungent Alcohol reacts in the presence of a catalyst, and the catalyst is selected from bisulfate, support type bisulfate, support type to toluene sulphur Acid and combination thereof.

Preferably, the technique is additionally included in removes isooctanol and/or catalyst after reaction, and it is different pungent to obtain aliphatic acid Ester crude product, it is preferred that as distill gained reaction mixture with remove the isooctanol and/or by be selected from filtering, pumping The method of filter, press filtration, centrifugation and sedimentation removes the catalyst.

It is taken off it is further preferred that the technique further includes the fatty acid isooctyl crude product to obtained by as adsorption method Acid treatment, obtains fatty acid isooctyl product, and preferred adsorbent is selected from activated carbon, aluminium oxide, diatomite, carclazyte, molecular sieve Or its combination.

Preferably, the reaction carries out under inert gas shielding.And further preferably in the reaction process The water for reacting generated is taken out of by the inert gas.

Preferably, the aliphatic acid is the main aliphatic acid for including saturated fatty acids more than 16 carbon, it is highly preferred that institute Aliphatic acid is stated as the main aliphatic acid comprising 16 carbon saturated fatty acids and/or 18 carbon saturated fatty acids, more preferably palm Acid or stearic acid.

Preferably, the isooctanol is 2- ethyl-hexanols.

Preferably, the molar ratio of the aliphatic acid and isooctanol is about 1:1.1 to about 1:2.0, more preferably from about 1:1.2 to about 1:1.8, particularly preferably about 1:1.3 to about 1:1.5.

Preferably, the dosage of the catalyst for aliphatic acid and isooctanol total weight about 0.01-5wt%, more preferably from about 0.05-2wt%。

Preferably, the bisulphate salt catalyst is selected from sodium bisulfate monobydrate, niter cake, sulfuric acid monohydrate hydrogen Potassium, potassium acid sulfate, ammonium hydrogen sulfate and combination thereof.

Preferably, the support type bisulphate salt catalyst be selected from support type niter cake, support type potassium acid sulfate with And combination thereof, more preferably the carrier used in loaded catalyst be selected from activated carbon, silica, silica gel, aluminium oxide, point Sub- sieve, carclazyte, diatomite and combination thereof.

On the other hand, the present invention provides bisulfate, support type bisulfate and/or support type p-methyl benzenesulfonic acid For be catalyzed aliphatic acid and isooctanol reaction purposes, preferred bisulfate be selected from sodium bisulfate monobydrate, niter cake, Sulfuric acid monohydrate hydrogen potassium, potassium acid sulfate, ammonium hydrogen sulfate and combination thereof；Preferred support type bisulfate is selected from load Type niter cake, support type potassium acid sulfate and combination thereof, the preferably carrier used in loaded catalyst are selected from activity Charcoal, silica, silica gel, aluminium oxide, molecular sieve, carclazyte, diatomite and combination thereof.

On the other hand, the present invention provides a kind of fatty acid isooctyls, which is characterized in that the aliphatic acid is main bag Aliphatic acid containing saturated fatty acids more than 16 carbon, and the hydroxyl value of the fatty acid isooctyl is less than 1mgKOH/g, acid value Not higher than 0.2mgKOH/g, Hazen colourities are less than 30.

Preferably, the fatty acid isooctyl is the fatty acid isooctyl prepared using above-mentioned present invention process.

Compared with prior art, at least one following technique effect can be realized using present invention process：

（1）High catalytic efficiency, conversion rate of fatty acid is increased to more than 99.8%, and product yield is increased to more than 95.9%；

（2）Isooctanol and catalyst amount are reduced, saves production cost；

（3）Used catalyst is corrosion-free to equipment, reduces equipment requirement；

（4）Reaction process does not have to water entrainer, reduces contamination of products, production process is environmentally friendly；

（5）Catalyst is easy to separate with product, remain less；Can be used filtering, centrifugation and sedimentation the methods of remove, because without The post processings such as alkali cleaning, washing are needed, waste water and easy to operate is not generated, and loss of product can be reduced so that different monooctyl ester yield It is further increased to more than 97%.

Specific embodiment

Technical solution and advantageous effect for a better understanding of the present invention, below in conjunction with embodiment to the preferred of the present invention Embodiment is described in more detail.It should be appreciated that these explanations are exemplary only, and should not be construed as with any side Formula limits the invention.

" scope " disclosed herein in the form of lower and upper limit, such as one or more lower limit in one or more The form of limit provides.Given range can be by selecting a lower limit and a upper limit to be defined, selected lower and upper limit Define the border of given range.All scopes limited in this way are included and can be combined, i.e., any lower limit can be with Any upper limit combines to form a scope.For example, listing the scope of 60-110 and 80-120 for special parameter, it is interpreted as The scope of 60-120 and 80-110 is also what is be contemplated that.In addition, if the upper limit that the lower limit listed is listed for 1 and 2 is 3,4 With 5, then following scope is all contemplated that：1-3,1-4,1-5,2-3,2-4 and 2-5.

Herein, unless otherwise indicated, numberical range " a-b " represents the breviary of the arbitrary real combinings between a to b It represents, wherein a and b are real numbers.Such as numberical range " 0-5 " represent all to have listed herein it is complete between " 0-5 " Portion's real number, " 0-5 " are that the breviary of these combinations of values represents.

It herein, unless otherwise indicated, can between the content range of each component of composition and its preferred scope New technical solution is formed to be mutually combined.

Herein, unless otherwise indicated, term " it is combined " or " combination thereof " represent listed each selection Any combination of element, such as the combination of two kinds, three kinds, four kinds and the selection element until most probable number, such as mix Object.

Herein, unless otherwise indicated, all " part " and percentage（%）All it is on the basis of weight, that is, weighs Measure part and wt%.

Herein, unless otherwise indicated, the sum of percentage composition of each component is 100% in all compositions.

If be not specifically stated, the term " a kind of (a) " used in this specification refers to " at least one (a) ".

If be not specifically stated, all percentages of the invention provided（Such as weight percent）Benchmark be all described group Close the total amount of object（Such as total weight）.

Herein, unless otherwise indicated, the ratio of each component or weight are all referring to dry weight.

Herein, unless otherwise indicated, all embodiments and preferred embodiment mentioned in this article can be with It is mutually combined to form new technical solution.

Herein, unless otherwise indicated, all technical characteristics and preferred feature mentioned in this article can be mutual Combination forms new technical solution.

Herein, unless otherwise indicated, all steps mentioned in this article can be carried out sequentially, can also at random into Row, it is preferred that being that order carries out.For example, the method includes the steps（a）With（b）, represent that the method may include order Progress the step of（a）With（b）, the step of order carries out can also be included（b）With（a）.It may also include for example, mentioning the method Step（c）, represent step（c）Can the method be added to random order, for example, the method may include steps（a）、 （b）With（c）, may also comprise step（a）、（c）With（b）, step can also be included（c）、（a）With（b）Deng.

Herein, unless otherwise indicated, term " comprising ", "comprising", " containing ", " having " and similar word represent It is open, but be also understood to specifically disclose enclosed situation simultaneously.For example, " comprising " represents to include not There is the other element listed, but also specifically disclose the situation for only including listed element simultaneously.

Herein, unless otherwise indicated, the specific steps described in embodiment, concrete numerical value and specific substance can It is combined with other features of specification other parts.For example, the specification content of the invention or specific embodiment part mention reaction Temperature for 10-100 DEG C, and the specific reaction temperature that embodiment is recorded is 20 DEG C, then it is considered that specific public affairs herein 10-20 DEG C of scope or 20-100 DEG C of scope are opened, and the scope can be with other feature knots of specification other parts Collectively form new technical solution.

Herein, unless otherwise indicated, term " mainly including " and " key component " represent content more than 90%, It is preferred that more than 95%, more preferable more than 98%, particularly preferred more than 99%.

In the present invention, aliphatic acid can be aliphatic acid commonly used in the art, such as saturated fatty acid, including but it is unlimited In：Dodecanoic acid（Lauric acid）, tetradecanoic acid（Myristic acid）, hexadecanoic acid（Palmitic acid）, octadecanoid acid（Stearic acid）, 20 Alkanoic acid（Arachidic acid）, behenic acid（Behenic acid）, lignoceric acid（Lignoceric acid）And hexacosoic acid（Cerinic acid）；Single insatiable hunger And aliphatic acid, include but not limited to：Nutmeg oleic acid, palmitoleic acid, oleic acid；Polyunsaturated fatty acid includes but not limited to：It is sub- Oleic acid, leukotrienes, arachidonic acid.

Herein, unless otherwise indicated, term " saturated fatty acids more than 16 carbon " refer to 16 and more than Carbon number saturated fatty acid, include but not limited to：The saturated fatty acid of 16 carbon, 18 carbon, 20 carbon etc. and Combination thereof.In the present invention, it is preferred to use 16 carbon and/or the saturated fatty acid of 18 carbon.

Herein, unless otherwise indicated, term " palmitic acid " represents to be referred to as, it can both represent pure saturation 16 Carbon fatty acid, can also represent that this field is conventionally recognized by with 16 carbon fatty acid of saturation fatty acid composition as main component Object, such as palmitic acid 1698.

Similarly, herein, unless otherwise indicated, term " stearic acid " represents to be referred to as, it can both represent pure 18 carbon fatty acid of saturation, can also represent that this field is conventionally recognized by with 18 carbon fatty acid of saturation fat as main component Acid composition, such as stearic acid 1890 and stearic acid 1840.

Herein, unless otherwise indicated, term " active matter " refers to the reaction to aliphatic acid and isooctanol and mainly urges The substance of change effect, not including catalyst carrier.

Herein, unless otherwise indicated, the dosage of catalyst is counted on the basis of active matter, such as catalyst Dosage is represented for the about 0.01-5wt% of aliphatic acid and isooctanol total weight being included in used catalyst (such as loaded catalyst) Active matter total amount is about 0.01-5wt% compared with the total weight of aliphatic acid and isooctanol.

Herein, unless otherwise indicated, term " carrying capacity of active matter " refers to active phase pair in loaded catalyst In the weight percent of carrier.

As described above, on the one hand, the present invention provides the preparation process of fatty acid isooctyl, including making aliphatic acid and different pungent Alcohol reacts in the presence of a catalyst, wherein the catalyst is selected from bisulfate, support type bisulfate, support type to first Benzene sulfonic acid and combination thereof.

In a preferred embodiment, in order to ensure the different not oxidized discoloration of monooctyl ester product, the reaction is in inert gas Protection is lower to be carried out.It is further preferred that the inert gas is selected from nitrogen, helium and argon gas, particularly preferred nitrogen.

In order to which the progress for being conducive to reaction preferably removes the water generated in reaction process in time.In preferred embodiment In, to prevent addition water entrainer polluted product and environment or negative pressure water removal from taking raw material out of, the band by the way of logical inert gas The water being born.It is further preferred that the inert gas is selected from nitrogen, helium and argon gas, particularly preferred nitrogen.

In particularly preferred embodiments, the reaction carries out under inert gas shielding and passes through the inert gas band Go out the water of reaction generation.It is further preferred that the inert gas is selected from nitrogen, helium and argon gas, particularly preferred nitrogen.

In a preferred embodiment, the molar ratio of the aliphatic acid and isooctanol is about 1:1.1 to about 1:2.0, it is more excellent Choosing about 1:1.2 to about 1:1.8, particularly preferably about 1:1.3 to about 1:1.5.

In particularly preferred embodiments, the molar ratio of the aliphatic acid and isooctanol is about 1:1.1、1:1.2、1: 1.3、1:1.4、1:1.5、1:1.6、1:1.7、1:1.8、1:1.9 or 1:2.0.

In a preferred embodiment, the dosage of the catalyst is aliphatic acid and the about 0.01- of isooctanol total weight 5wt%, preferably from about 0.05-2wt%, more preferably from about 0.05wt% are to less than about 1wt%.

In further preferred embodiment, the dosage of the catalyst is aliphatic acid and the pact of isooctanol total weight 0.01 wt %、0.02 wt %、0.03 wt %、0.04 wt %、0.05 wt %、0.06 wt %、0.07 wt %、0.08 wt %、0.09 wt %、0.1 wt %、0.15 wt %、0.2 wt %、0.25 wt %、0.3 wt %、0.35 wt %、0.4 wt %、0.45 wt %、0.5 wt %、0.55 wt %、0.6 wt %、0.65 wt %、0.7 wt %、0.75 wt %、0.8 wt %、0.85 wt %、0.9 wt %、0.95 wt %、1 wt %、1.1wt %、1.2 wt %、1.3 wt %、1.4 wt %、1.5 wt %、1.6 wt %、1.7 wt %、1.8 wt %、1.9 wt %、2 wt %、2.1 wt %、2.2 wt %、2.3 wt %、 2.4 wt %、2.5 wt %、2.6 wt %、2.7 wt %、2.8 wt %、2.9 wt %、3 wt %、3.1 wt %、3.2 wt %、3.3 wt %、3.4 wt %、3.5 wt %、3.6 wt %、3.7 wt %、3.8 wt %、3.9 wt %、4 wt %、4.1 wt %、4.2 wt %、4.3 wt %、4.4 wt %、4.5 wt %、4.6 wt %、4.7 wt %、4.8 wt %、4.9 wt % Or 5 wt %.

In a preferred embodiment, the reaction temperature of the reaction is about 100-200 DEG C, more preferably from about 130-170 DEG C.

In particularly preferred embodiments, the reaction temperature of the reaction be about 100 DEG C, 101 DEG C, 102 DEG C, 103 DEG C, 104℃、105℃、106℃、107℃、108℃、109℃、110℃、111℃、112℃、113℃、114℃、115℃、116 ℃、117℃、118℃、119℃、120℃、121℃、122℃、123℃、124℃、125℃、126℃、127℃、128℃、 129℃、130℃、131℃、132℃、133℃、134℃、135℃、136℃、137℃、138℃、139℃、140℃、141 ℃、142℃、143℃、144℃、145℃、146℃、147℃、148℃、149℃、150℃、151℃、152℃、153℃、 154℃、155℃、156℃、157℃、158℃、159℃、160℃、161℃、162℃、163℃、164℃、165℃、166 ℃、167℃、168℃、169℃、170℃、171℃、172℃、173℃、174℃、175℃、176℃、177℃、178℃、 179℃、180℃、181℃、182℃、183℃、184℃、185℃、186℃、187℃、188℃、189℃、190℃、191 DEG C, 192 DEG C, 193 DEG C, 194 DEG C, 195 DEG C, 196 DEG C, 197 DEG C, 198 DEG C, 199 DEG C or 200 DEG C.

It is further preferred that the reaction time of the reaction is about 1-10h, particularly preferably about 1.5-6h.

In a preferred embodiment, present invention process is additionally included in removes isooctanol and/or catalyst after reaction, Obtain fatty acid isooctyl crude product, it is preferred that as distill gained reaction mixture with remove the isooctanol and/or lead to It crosses the method selected from filtering, suction filtration, press filtration, centrifugation and sedimentation and removes the catalyst.

In further preferred embodiment, the temperature used during excessive isooctanol is distilled for about 60-200 DEG C, pressure It is about 2 millibars to about 1 bar；More preferably described temperature is about 60-180 DEG C, and pressure is about 2-600 millibars；Particularly preferably institute It is about 80-120 DEG C to state temperature, and pressure is about 8-60 millibars.

In order to further remove the minute quantity catalyst of dissolving in the product, in further preferred embodiment, this Invented technology is further included carries out depickling processing to gained fatty acid isooctyl crude product, obtains fatty acid isooctyl product.Due to The residual quantity of catalyst is less than 2/10000ths in present invention process, because without taking the washing depickling in traditional handicraft, to keep away Exempt to generate a large amount of waste water.Therefore, in embodiment still more preferably, the depickling processing is carried out by absorption method. Adsorbent workable for heretofore described depickling processing is well known to those skilled in the art, and preferred adsorbent, which is selected from, lives The materials such as property charcoal, aluminium oxide, diatomite, carclazyte or molecular sieve；The adsorbent amount can be according to being actually adjusted, for this Known to the those of ordinary skill in field, particularly preferably the adsorbent amount is more than 0% to about 2% for weight of crude product, For example, the adsorbent amount for weight of crude product 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%th, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% or 2%.

In some preferred embodiments, the aliphatic acid used in the present invention is mainly comprising 16 carbon saturated fatty acid And/or 18 carbon saturated fatty acid aliphatic acid, more preferably palmitic acid or stearic acid.

In a preferred embodiment, the isooctanol used in the present invention is 2- ethyl-hexanols.

In some preferred embodiments, it is used in bisulfate and support type bisulfate of the present invention Bisulfate can select using conventional use of bisulfate in this field, be preferably disulfate, such as can be with Including but not limited to：Sodium bisulfate monobydrate, niter cake, sulfuric acid monohydrate hydrogen potassium, potassium acid sulfate, ammonium hydrogen sulfate and they Combination.

In some preferred embodiments, the present invention used in catalyst be selected from sodium bisulfate monobydrate, niter cake, Sulfuric acid monohydrate hydrogen potassium, potassium acid sulfate, ammonium hydrogen sulfate and combination thereof.

In some preferred embodiments, the catalyst used in the present invention is selected from support type bisulfate and support type P-methyl benzenesulfonic acid, more preferable support type bisulfate, further preferred support type niter cake and support type potassium acid sulfate, it is special Not preferred support type niter cake.

In a preferred embodiment, the carrier used in loaded catalyst of the invention is selected from activated carbon, silica And combination thereof.It is particularly preferred that in terms of carrier total amount, the carrying capacity of active matter is about 10- in the loaded catalyst 150wt%。

In a preferred embodiment, the hydroxyl value of the fatty acid isooctyl product obtained by present invention process is less than 1mgKOH/ G, acid value are not higher than 0.2mgKOH/g, and Hazen colourities are less than 30.It is highly preferred that the hydroxyl value of gained fatty acid isooctyl product is small In 0.2mgKOH/g.

In particularly preferred embodiments, the preparation method of the loaded catalyst comprises the following steps：

A) active matter with restriction 2wt% to saturated concentration（Such as bisulfate or p-methyl benzenesulfonic acid）Aqueous solution；

B) weigh the carrier of respective amount, add in a) obtained by solution in, stir evenly, impregnate about 2-48h；And

C) filter, filter cake is in about 100-200 DEG C drying about 2-10h.

In particularly preferred embodiments, fatty acid isooctyl preparation process of the invention comprises the following steps：

1) aliphatic acid, isooctanol and catalyst mixing and are reacted in a heated condition in the reactor；

2) isooctanol and/or catalyst are removed after reaction, obtain fatty acid isooctyl crude product；And

3) depickling is carried out to gained crude product, obtains fatty acid isooctyl finished product.

It is further preferred that step 1）The reactor includes the reactor of all kinds of suitable esterifications.

It is further preferred that step 1）Reaction carried out under inert gas shielding and reaction taken out of by the inert gas The water of generation.It is further preferred that the inert gas is selected from nitrogen, helium and argon gas, particularly preferred nitrogen.

It is further preferred that step 1）The aliphatic acid of the reaction and the molar ratio of isooctanol are about 1:1.1 to about 1: 2.0, preferably from about 1:1.2 to about 1:1.8, more preferably from about 1:1.3 to about 1:1.5.

It is further preferred that step 1）The catalyst amount of the reaction is aliphatic acid and the pact of isooctanol total weight 0.01-5wt%, preferably from about 0.05-2wt%, more preferably from about 0.1wt% are to less than about 1wt%.

It is further preferred that step 1）The reaction temperature of the reaction is about 100-200 DEG C, more preferably from about 130-170 DEG C. It is further preferred that the reaction time of the reaction is about 1-10h, particularly preferably about 1.5-6h.

It is further preferred that step 2）In as obtained by distillation reaction mixture to remove the isooctanol；It is further excellent Selection of land, the temperature of the distillation isooctanol is about 60-200 DEG C, and pressure is about 2 millibars to about 1 bar；More preferably described temperature is About 60-180 DEG C, pressure is about 2-600 millibars；Particularly preferably described temperature is about 80-120 DEG C, and pressure is about 8-60 millibars.

It is further preferred that step 2）The method for removing catalyst is selected from filtering, suction filtration, press filtration, centrifugation and sedimentation.

It is further preferred that step 3）The method of the crude product depickling is adsorption deacidification method, is still more preferably adsorbed Agent is selected from the materials such as activated carbon, aluminium oxide, diatomite, carclazyte or molecular sieve, particularly preferably the adsorbent amount is crude product Weight is more than 0% to about 2%.

On the other hand, the present invention provides a kind of fatty acid isooctyls, which is characterized in that the aliphatic acid is mainly to include The aliphatic acid of saturated fatty acids more than 16 carbon, and the hydroxyl value of the fatty acid isooctyl is less than 1mgKOH/g, and acid value is not Higher than 0.2mgKOH/g, Hazen colourities are less than 30.

In a preferred embodiment, the fatty acid isooctyl is the aliphatic acid prepared using above-mentioned present invention process Different monooctyl ester.

In some preferred embodiments, the hydroxyl value of the fatty acid isooctyl is less than 0.2mgKOH/g.

In order to make statement more succinct, various preferred embodiments of the invention are separately individually to describe in the description , it will be recognized to those skilled in the art that in the case where not contradicting, the technical characteristic of each preferred embodiment can be with It reconfigures and to form other or embodiment still more preferably, these embodiments and should be considered as by this civilization It really discloses and falls within the scope of protection of the present invention.

Embodiment

Illustrative description is made to the present invention by the following examples, it should be understood that these embodiments are merely to illustrate mesh Without being construed as limiting the invention.

Reagent and detection method

1）All kinds of aliphatic acid used are by beneficial sea in all embodiments and comparative example（Lianyun Harbour）Oiling industry has Limit company provides.Specifically, the carbon composition of aliphatic acid used is as shown in table 1 below in embodiment.

The composition of 1. aliphatic acid of table

Note：The aliphatic acid titles of a herein represent to be referred to as；

The aliphatic acid titles of b herein refer in particular to the pure fatty acid with specific carbon number.

2）In addition, in the present invention, the index of correlation of products obtained therefrom is detected by following detection method：

Product acid value measuring method：AOCS Te 1a-64；

Product hydroxy value measuring method：AOCS Tl1a-64；

Product color assay method：AOCS Cc 13e-92；

Esterification yield computational methods：（Acid value/initial acid value after 1- reactions）×100%；

Yield computational methods：（Final product weight/theoretical yield）×100%.

Such as illustrate without other, percentage used is weight percentage in all embodiments and comparative example, and institute Catalyst amount is with actives basis, such as the activated carbon supported niter cakes of 0.05wt%, refers to activated carbon supported niter cake Additive amount be that the weight of contained active matter niter cake compared with the total weight of aliphatic acid and isooctanol raw material is 0.05%.

Comparative example 1

Into the four-hole boiling flask of the 250mL equipped with blender, 0.25mol palmitic acids are added in（1698）, 0.325mol it is different pungent Alcohol and 0.5wt% p-methyl benzenesulfonic acid mixings, nitrogen are protected, and temperature is risen to 150 DEG C after heating and melting, keep the temperature 1.5h, and reaction terminates Vacuum distillation, removes excessive alcohol；It is cooled to room temperature, by reacting liquid filtering, obtains crude product acid value as 1.30mgKOH/g.With The sodium hydroxide solution of 50mL 10% is washed, then is washed for 2 times with 100mL moisture, vacuum dehydration, add in 0.5wt% activated carbon and The atlapulgite of 0.5wt% stirs 1h, isobutyl palmitate product is obtained by filtration.The acid value of product be 0.17mgKOH/g, hydroxyl value For 0.2mgKOH/g, color and luster 35.Esterification yield is 99.69%, yield 92.0%.

Embodiment 1

In the four-hole boiling flask of 250mL equipped with blender, the palmitic acid of 0.25mol is added in（1698）It is different with 0.325mol Octanol adds in the activated carbon supported niter cake of 0.05wt%, leads to nitrogen protection, rises to reaction temperature after reactant thawing It 150 DEG C, after keeping the temperature 5h, is evaporated under reduced pressure, removes excessive alcohol.It is cooled to room temperature, filters, obtaining crude product acid value is 0.15mgKOH/g.Crude product with 200mL moisture is washed for 3 times, vacuum dehydration, add in the activated carbon of 0.2wt%, stir 1h, filtering Obtain isobutyl palmitate product.Product acid value be 0.06mgKOH/g, hydroxyl value 0.2mgKOH/g, color and luster 11.Esterification yield is 99.96%, yield 95.9%.

Embodiment 2

In the four-hole boiling flask of the 250mL equipped with blender, 0.25mol palmitic acids are added in（1698）, 0.325mol it is different pungent Alcohol and the activated carbon supported niter cake mixings of 0.05wt%, nitrogen are protected, and temperature are risen to 150 DEG C of heat preservation 5h after heating and melting, instead It should terminate to be evaporated under reduced pressure, remove excessive alcohol.It is cooled to room temperature, by reacting liquid filtering, obtaining crude product acid value is 0.15mgKOH/g.The activated carbon of 0.2wt% is added in crude product, 1h is stirred, isobutyl palmitate product is obtained by filtration.Product Acid value for 0.06mgKOH/g, hydroxyl value 0.2mgKOH/g, color and luster 7.Esterification yield is 99.96%, yield 98.7%.

Embodiment 3

Concrete operation method is consistent with embodiment 2.Difference is that it is 0.3mol to add in isooctanol, keeps the temperature 6h, after filtering It is 0.20mgKOH/g to crude product acid value.The acid value of product is 0.13mgKOH/g after same operation depickling, and hydroxyl value is 0.2mgKOH/g, color and luster 10.Esterification yield is 99.91%, yield 98.7%.

Embodiment 4

Concrete operation method is consistent with embodiment 2.Difference is 170 DEG C of reaction temperature, and soaking time 4h is obtained after filtering Crude product acid value is 0.15mgKOH/g.The acid value of product is 0.07mgKOH/g, hydroxyl value 0.2mgKOH/ after same operation depickling G, color and luster 18.Esterification yield is 99.95%, yield 98.7%.

Embodiment 5

Concrete operation method is consistent with embodiment 2.Difference is isooctanol for 0.35mol, 140 DEG C of reaction temperature, filtering After obtain crude product acid value as 0.17mgKOH/g.The acid value of product is 0.07mgKOH/g after same operation depickling, and hydroxyl value is 0.2mgKOH/g, color and luster 5.Esterification yield is 99.95%, yield 98.7%.

Embodiment 6

Concrete operation method is consistent with embodiment 2.Difference is first to react 2h at 110 DEG C, then is warming up to 160 DEG C of reactions 4h obtains crude product acid value as 0.21mgKOH/g after filtering.After same operation depickling the acid value of product be 0.09mgKOH/g, hydroxyl It is worth for 0.2mgKOH/g, color and luster 9.Esterification yield is 99.94%, yield 98.7%.

Embodiment 7

Concrete operation method is consistent with embodiment 2.Difference is that it is 0.3mol to add in isooctanol, adds in activated carbon supported sulphur Sour hydrogen sodium amount is 0.4wt%, and reaction temperature is 140 DEG C, keeps the temperature 1.5h, and crude product acid value is obtained after filtering as 0.19mgKOH/g. After same operation depickling the acid value of product be 0.10mgKOH/g, hydroxyl value 0.2mgKOH/g, color and luster 25.Esterification yield is 99.93%, yield 98.2%.

Embodiment 8

Concrete operation method is consistent with embodiment 2.Difference is catalyst for the activated carbon supported potassium acid sulfates of 0.05wt%, Crude product acid value is obtained after filtering as 0.19mgKOH/g.After same operation depickling the acid value of product be 0.06mgKOH/g, hydroxyl value For 0.2mgKOH/g, color and luster 9.Esterification yield is 99.87%, yield 98.7%.

Embodiment 9

Concrete operation method is consistent with embodiment 2.Difference is catalyst for 0.3wt% sodium bisulfate monobydrates, heat preservation 3h obtains crude product acid value as 0.87mgKOH/g after filtering.Add in 1wt% activated carbon, stir 1h, filter palmitic acid is different pungent Ester product.Product acid value be 0.12mgKOH/g, hydroxyl value 0.2mgKOH/g, color and luster 17.Esterification yield is 99.92%, yield 97.3%。

Embodiment 10

Concrete operation method is consistent with embodiment 7.Difference is catalyst for 0.05wt% sodium bisulfate monobydrates, heat preservation 6h obtains crude product acid value as 0.28mgKOH/g after filtering.Add in 0.2wt% activated carbon, stir 1h, filter palmitic acid is different Monooctyl ester product.Product acid value be 0.14mgKOH/g, hydroxyl value 0.2mgKOH/g, color and luster 17.Esterification yield is 99.91%, yield 98.7%。

Embodiment 11

Concrete operation method is consistent with embodiment 8.Difference is that catalyst for anhydrous slufuric acid hydrogen sodium, keeps the temperature 6h, after filtering Crude product acid value is obtained as 0.28mgKOH/g.The activated carbon of 0.2wt% is added in, 1h is stirred, filters to obtain isobutyl palmitate product. Product acid value be 0.10mgKOH/g, hydroxyl value 0.2mgKOH/g, color and luster 17.Esterification yield is 99.93%, yield 98.7%.

Embodiment 12

Concrete operation method is consistent with embodiment 7.Difference is that catalyst is ammonium hydrogen sulfate.Crude product acid value is 0.65mgKOH/g, after same treatment operation, the acid value of product is 0.12mgKOH/g, hydroxyl value 0.2mgKOH/g, color and luster 18. Esterification yield is 99.92%, yield 97.7%.

Embodiment 13

Concrete operation method is consistent with embodiment 2.Difference is that aliphatic acid used is stearic acid（1890）, obtained after filtering Crude product acid value is 0.16mgKOH/g.Product acid value 0.08mgKOH/g after same operation depickling, hydroxyl value 0.2mgKOH/g, color Pool is 23.Esterification yield is 99.94%, yield 98.7%.

Embodiment 14

Concrete operation method is consistent with embodiment 2.Difference is that aliphatic acid used is stearic acid（1840）, obtained after filtering Crude product acid value is 0.16mgKOH/g.Product acid value 0.08mgKOH/g after same operation depickling, hydroxyl value 0.2mgKOH/g, color Pool is 18.Esterification yield is 99.94%, yield 98.7%.

Embodiment 15

Concrete operation method is consistent with embodiment 2.Difference is that catalyst is activated carbon supported to toluene sulphur for 0.15wt% Acid keeps the temperature 3h, and crude product acid value is obtained after filtering as 0.15mgKOH/g.The acid value of product is after same operation depickling 0.08mgKOH/g, hydroxyl value 0.2mgKOH/g, color and luster 15.Esterification yield is 99.94%, yield 98.7%.

Embodiment 16

Concrete operation method is consistent with embodiment 2.Difference is that catalyst is silicon dioxide carried to toluene sulphur for 0.5wt% Acid.Crude product acid value is 0.16mgKOH/g, and after same treatment operation, the acid value of product is 0.10mgKOH/g, and hydroxyl value is 0.2mgKOH/g, color and luster 18.Esterification yield is 99.93%, yield 98.7%.

Embodiment 17

Concrete operation method is consistent with embodiment 2.Difference is that catalyst is the activated carbon supported p-methyl benzenesulfonic acid of 0.1wt% With the activated carbon supported niter cakes of 0.03wt%, 3h is kept the temperature, crude product acid value is obtained after filtering as 0.15mgKOH/g.Same operation After depickling the acid value of product be 0.08mgKOH/g, hydroxyl value 0.2mgKOH/g, color and luster 15.Esterification yield is 99.94%, yield 98.7%。

According to the result of above-described embodiment：

1）The esterification yield of aliphatic acid can be increased to more than 99.8% even up to by 99.69% using the method for the present invention 99.96%, and fatty acid isooctyl yield is increased to more than 95.9% even up to 98.7% by 92.0%, the color and luster of product by 35APHA is down to less than 23 even up to 5；

2）Production can be further improved by substituting WATER-WASHING METHOD removing remainder catalyst using filtration method etc. in the methods of the invention Object yield is increased to more than 97% by 95.9%；

3）In the case where ensuring catalytic efficiency, the appropriate catalyst amount that reduces can reduce catalyst residual, and then subtract Quantity of sorbent used, so as to reduce loss of product, can also reduce product color during few adsorption deacidification processing,

The preferred embodiment of the present invention is specifically described above by reference to embodiment, however these descriptions are only explanation Property and not restrictive.Those skilled in the art, can be excellent to these on the premise of without departing from spirit and scope of the present invention Embodiment is selected to make various obvious change and modification, these changes or amended embodiment still fall within this hair In bright protection domain.

Claims (17)

1. the preparation process of fatty acid isooctyl, including aliphatic acid and isooctanol is made to react in the presence of a catalyst, wherein described Catalyst is selected from bisulfate, support type bisulfate, support type p-methyl benzenesulfonic acid or combination thereof, wherein described Aliphatic acid aliphatic acid chosen from the followings：Dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoid acid, arachic acid, 22 Alkanoic acid, lignoceric acid, hexacosoic acid, nutmeg oleic acid, palmitoleic acid, oleic acid, linoleic acid, leukotrienes and arachidonic Acid, wherein the reaction carries out under the following conditions：The molar ratio of the aliphatic acid and isooctanol is 1:1.1 to 1:2.0, it is described The dosage of catalyst is extremely less than 1wt% for the 0.05wt% of aliphatic acid and isooctanol total weight, and reaction temperature is 100-200 DEG C.

2. technique according to claim 1 is additionally included in and removes isooctanol and/or catalyst after reaction, obtains fat The different monooctyl ester crude product of fat acid.

3. technique according to claim 2, wherein as obtained by distillation reaction mixture come remove the isooctanol and/ Or remove the catalyst by being selected from the method for filtering, suction filtration, press filtration, centrifugation and sedimentation.

4. the technique according to Claims 2 or 3, further include as adsorption method to obtained by fatty acid isooctyl crude product into Row depickling is handled, and obtains fatty acid isooctyl product.

5. technique according to claim 4, wherein adsorbent used be selected from activated carbon, aluminium oxide, diatomite, carclazyte, Molecular sieve or combination thereof.

6. technique according to any one of claim 1-3, wherein the reaction carries out under inert gas shielding, and The water for reacting generated is taken out of by the inert gas in the reaction process.

7. technique according to any one of claim 1-3, wherein the aliphatic acid is to include saturations more than 16 carbon The aliphatic acid of aliphatic acid.

8. technique according to any one of claim 1-3, wherein the aliphatic acid is to include 16 carbon saturated fatty acids And/or 18 carbon saturated fatty acid aliphatic acid.

9. technique according to any one of claim 1-3, wherein the aliphatic acid is palmitic acid or stearic acid.

10. technique according to any one of claim 1-3, wherein the molar ratio of the aliphatic acid and isooctanol is 1: 1.2 to 1:1.8.

11. technique according to any one of claim 1-3, wherein the molar ratio of the aliphatic acid and isooctanol is 1: 1.3 to 1:1.5.

12. technique according to any one of claim 1-3, wherein the dosage of the catalyst is aliphatic acid and isooctanol The 0.05-0.95wt% of total weight.

13. technique according to any one of claim 1-3, wherein the dosage of the catalyst is aliphatic acid and isooctanol The 0.05-0.6wt% of total weight.

14. technique according to any one of claim 1-3, wherein the bisulfate is selected from sulfuric acid monohydrate hydrogen Sodium, niter cake, sulfuric acid monohydrate hydrogen potassium, potassium acid sulfate, ammonium hydrogen sulfate or combination thereof；The support type bisulphate Salt is selected from support type niter cake, support type potassium acid sulfate or combination thereof.

15. the carrier used in technique according to claim 14, wherein loaded catalyst is selected from activated carbon, titanium dioxide Silicon, silica gel, aluminium oxide, molecular sieve, carclazyte, diatomite or combination thereof.

16. bisulfate, support type bisulfate and/or support type p-methyl benzenesulfonic acid are used to be catalyzed aliphatic acid and isooctanol Reaction purposes, wherein the bisulfate be selected from sodium bisulfate monobydrate, niter cake, sulfuric acid monohydrate hydrogen potassium, sulphur Potassium hydrogen phthalate, ammonium hydrogen sulfate or combination thereof；The support type bisulfate is selected from support type niter cake, support type sulphur Potassium hydrogen phthalate or combination thereof, and the carrier used in loaded catalyst be selected from activated carbon, silica, silica gel, aluminium oxide, Molecular sieve, carclazyte, diatomite or combination thereof, wherein aliphatic acid aliphatic acid chosen from the followings：Dodecanoic acid, ten Four alkanoic acids, hexadecanoic acid, octadecanoid acid, arachic acid, behenic acid, lignoceric acid, hexacosoic acid, mace oil Acid, palmitoleic acid, oleic acid, linoleic acid, leukotrienes and arachidonic acid, wherein the reaction carries out under the following conditions：It is described The molar ratio of aliphatic acid and isooctanol is 1:1.1 to 1:2.0, the dosage of the catalyst is aliphatic acid and isooctanol total weight 0.05wt% is extremely less than 1wt%, and reaction temperature is 100-200 DEG C.

A kind of 17. fatty acid isooctyl that technique as any one of claim 1-15 is prepared, which is characterized in that institute It is the aliphatic acid for including saturated fatty acids more than 16 carbon to state aliphatic acid, and the hydroxyl value of the fatty acid isooctyl is less than 1mgKOH/g, acid value are not higher than 0.2mgKOH/g, and Hazen colourities are less than 30.