CN103965035A - Refining method of long-chain binary acid - Google Patents
Refining method of long-chain binary acid Download PDFInfo
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- CN103965035A CN103965035A CN201310035603.0A CN201310035603A CN103965035A CN 103965035 A CN103965035 A CN 103965035A CN 201310035603 A CN201310035603 A CN 201310035603A CN 103965035 A CN103965035 A CN 103965035A
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- chain biatomic
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- 238000000034 method Methods 0.000 title claims abstract description 95
- 238000007670 refining Methods 0.000 title abstract description 6
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- 239000012043 crude product Substances 0.000 claims abstract description 65
- 239000000047 product Substances 0.000 claims abstract description 59
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- 238000002360 preparation method Methods 0.000 claims description 20
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- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 6
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- 150000007513 acids Chemical class 0.000 claims 4
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
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- 238000002834 transmittance Methods 0.000 description 16
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- 229910052757 nitrogen Inorganic materials 0.000 description 15
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- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
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- OKVWYBALHQFVFP-UHFFFAOYSA-N 2,3,3-trimethylpentane Chemical compound CCC(C)(C)C(C)C OKVWYBALHQFVFP-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 102100028175 Abasic site processing protein HMCES Human genes 0.000 description 1
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a refining method of a long-chain binary acid. The refining method comprises the following steps of 1, carrying out mixing heating dissolution on a long-chain binary acid crude product and alkane, 2, separating a clear phase, and 3, carrying out cooling crystallization or precipitation to obtain the long-chain binary acid product. The refining method realizes high-yield and low-energy consumption production of the long-chain binary acid product.
Description
Technical field
The present invention relates to a kind of process for purification.Specifically, the present invention relates to the process for purification of long-chain biatomic acid.
Background technology
Long-chain biatomic acid is the base monomer raw material of a series of synthetic materialss, long-chain biatomic acid and derivative monomer thereof can be for the production of nylon, polycarbonate, powder coating, spices, hot melt adhesive, extraordinary lubricants etc., are the important source material of the products such as synthetic perfume, engineering plastics, cold resistant plasticizer, senior lubricant and polyamide hot.
In the preparation process of long-chain biatomic acid, conventionally in reaction solution, first form long-chain biatomic acid salt, need be to carrying out a series of processing containing the reaction solution of long-chain biatomic acid salt to obtain long-chain biatomic acid product.
Produce in the process of long-chain biatomic acid at biological fermentation process, in the fermented liquid after fermentation ends, except comprising long-chain biatomic acid salt, also comprise thalline and other impurity, as residual alkane or lipid acid.Need to process to obtain long-chain biatomic acid to fermented liquid.
The method that obtains at present long-chain biatomic acid from fermented liquid comprises that first carrying out the pre-treatment such as degerming, decolouring, acidifying, filtration obtains primary products, then further carries out the processing such as recrystallization, decolouring, washing, and this method steps is tediously long, and production cost is higher.
In patent documentation 1, disclose a kind of production method of positive long-chain biatomic acid, wherein fermented liquid has been carried out to ceramic membrane except a series of processing such as thalline, activated carbon decolorizing, mineral acid acidifying, Plate Filtration, solvent crystallizations, to obtain dicarboxylic acid product.There is following shortcoming in this treatment process: 1) need to consume a large amount of gacs, the usage quantity of gac is up to 5 ~ 10% of product, not recyclable because of the gac after decolouring, causes the wasting of resources and environmental pollution; 2) the residual diprotic acid in crystalline mother solution reclaims difficulty, and crystallization yield is low; 3) crystalline mother solution evaporation needs lot of energy, and energy consumption is large.
In patent documentation 2, disclose from the filtrate of separating thallus and separated out long-chain biatomic acid with mineral acid, then separated out diprotic acid with Aromatics Extractive Project.Mix with this extract by polyvalent alcohol or containing the organism of more than two aldehyde radical, the impurity in extract is optionally transferred in non-aromatics solvent, finally crystallization diprotic acid from extract.This technique is used two or more solvents to extract, and two portions solvent need to be processed respectively, complex technical process, unstable product quality.
People wish to develop with high yield, less energy-consumption always and extract and the novel method of refining long-chain biatomic acid.
Prior art document
Patent documentation 1: Chinese patent ZL200410018255.7
Patent documentation 2: Japanese Patent examined patent publication 63-022797.
Summary of the invention
The object of this invention is to provide a kind of process for purification of long-chain biatomic acid, can obtain long-chain biatomic acid product with high yield, less energy-consumption.
The inventor is in view of problems of the prior art, process for purification to long-chain biatomic acid conducts in-depth research, and found that, by using specific organic solvent as recrystallization solvent, can obtain long-chain biatomic acid product with high yield, less energy-consumption, thereby complete the present invention., the present invention is:
[1] process for purification for long-chain biatomic acid, the method comprises the following steps:
1) long-chain biatomic acid crude product and alkane Hybrid Heating are dissolved;
2) isolate alkane solution; And
3) decrease temperature crystalline or separate out and obtain long-chain biatomic acid product.
[2] process for purification for long-chain biatomic acid, the method comprises the following steps:
1) long-chain biatomic acid crude product and alkane Hybrid Heating are dissolved;
2) isolate alkane solution;
3) decrease temperature crystalline or separate out and obtain long-chain biatomic acid product; And
4) utilize above-mentioned steps 3) in the crystalline mother solution that obtains as alkane solvent, repeat above step 1) to 3), obtain other long-chain biatomic acid product.
[3] process for purification of the long-chain biatomic acid described in above-mentioned [1] or [2], wherein, the long-chain biatomic acid fermentation broth extract that described long-chain biatomic acid crude product is Biological preparation.
[4] process for purification of the long-chain biatomic acid described in above-mentioned [3], wherein, described long-chain biatomic acid crude product obtains as follows: the direct acid precipitation of long-chain biatomic acid fermented liquid of described Biological preparation is also isolated; The long-chain biatomic acid fermented liquid of described Biological preparation acid precipitation being isolated again after activated carbon decolorizing, membrane filtration degerming; Or, after the direct acid precipitation of long-chain biatomic acid fermented liquid of described Biological preparation separation, then obtain after washing or high-temperature water processing.
[5] process for purification of the long-chain biatomic acid described in above-mentioned [1] or [2], wherein, described long-chain biatomic acid crude product is the by product obtaining in long-chain biatomic acid extraction or solvent crystallization process.
[6] process for purification of the long-chain biatomic acid described in above-mentioned [5], wherein, the source of described long-chain biatomic acid crude product is: the long-chain biatomic acid precipitation of long-chain biatomic acid sewage treatment plant; Or, the long-chain biatomic acid mixture obtaining after long-chain biatomic acid recrystallization mother liquor is dry.
[7] process for purification of the long-chain biatomic acid described in above-mentioned [1] or [2], wherein, described long-chain biatomic acid crude product obtains as follows: the direct acid precipitation gained of long-chain biatomic acid fermented liquid of described Biological preparation; Or the long-chain biatomic acid fermented liquid of described Biological preparation acid precipitation and obtaining again after activated carbon decolorizing, membrane filtration degerming.
[8] process for purification of the long-chain biatomic acid described in above-mentioned [1] or [2], wherein, the main component of described long-chain biatomic acid crude product is one or more the mixture in nonane diacid, sebacic acid, DC11, SL-AH, tridecanyldicarboxylic acid, DC14,15 carbon dicarboxylic acids, 16-dicarboxylic acid, DC17, DC18 or 9-alkene-18 carbon diacid.
[9] process for purification of the described long-chain biatomic acid in above-mentioned [1] or [2], wherein, described alkane is one or more the mixture in straight-chain paraffin or branched paraffin.
[10] process for purification of the long-chain biatomic acid described in above-mentioned [7], wherein, the boiling point of described alkane is the scope of 120 DEG C～350 DEG C, and fusing point is below 70 DEG C.
[11] process for purification of above-mentioned [8] described long-chain biatomic acid, wherein, described alkane is one or more the mixture in octane, nonane, decane, undecane, dodecane, tridecane, the tetradecane, pentadecane, n-Hexadecane or heptadecane.
[12] process for purification of the described long-chain biatomic acid in above-mentioned [1] or [2], wherein, step 1) in solvent temperature be 110～200 DEG C and lower than 5～10 DEG C of the boiling points of alkane or mixed alkanes.
[13] process for purification of the described long-chain biatomic acid in above-mentioned [1] or [2], wherein, step 2) in by toppling over, method centrifugal or that filter obtains alkane solution.
[14] process for purification of the described long-chain biatomic acid in above-mentioned [1] or [2], wherein, in step 1) long-chain biatomic acid crude product dissolve completely after, add activated carbon decolorizing, then obtain alkane solution.
Utilize above-mentioned process for purification of the present invention, can obtain long-chain biatomic acid product with high yield, less energy-consumption.Compared with process for purification in the past, can significantly reduce gac usage quantity or can not use gac, solvent evaporates and peculiar smell significantly reduce, and alkane mother liquor can be without evaporation and direct circulation uses, the energy consumption and the solvent consumption that reduce technique, product yield is improved.
Embodiment
Long-chain biatomic acid in the present invention refer to carboxyl at the two ends of carbochain, there is the saturated or unsaturated Straight chain diatomic acid of 9 to 18 carbon atoms.Particularly, long-chain biatomic acid is one or more the mixture in nonane diacid, sebacic acid, DC11, SL-AH, tridecanyldicarboxylic acid, DC14,15 carbon dicarboxylic acids, 16-dicarboxylic acid, DC17, DC18 or 9-alkene-18 carbon diacid.
Long-chain biatomic acid crude product in the present invention can be the long-chain biatomic acid fermentation broth extract of Biological preparation, and wherein contained impurity is relevant with zymotechnique and leaching process.The composition of impurity, include but not limited to, fatty, residual alkane, albumen, sugar, organic acid, inorganic salt etc., in some cases, special needs to be pointed out is, long-chain biatomic acid also may contain a large amount of short carbon chain diprotic acid or lipid acid, includes but not limited to diprotic acid, acetic acid, lauric acid, oleic acid of C4 ~ C8 etc.The existence of these impurity, has reduced the quality of long-chain biatomic acid product, has limited the range of application of long-chain biatomic acid.
Above-mentioned long-chain biatomic acid crude product can be: the direct acid precipitation of long-chain biatomic acid fermented liquid of Biological preparation is also isolated; The long-chain biatomic acid fermented liquid of Biological preparation is through certain processing, as obtained filtrate after the methods such as activated carbon decolorizing, membrane filtration degerming, then acid precipitation being isolated; Or, after the direct acid precipitation of long-chain biatomic acid fermented liquid of Biological preparation separation, then obtain after washing or high-temperature water processing; Etc..
Above-mentioned long-chain biatomic acid crude product can also come from the waste liquid that is rich in long-chain biatomic acid of discharging in fermentation, treating process, for example in long-chain biatomic acid product leaching process, obtain, include but not limited to the long-chain biatomic acid mixture that long-chain biatomic acid recrystallization mother liquor obtains after dry, for example long-chain biatomic acid sewage treatment plant precipitates the long-chain biatomic acid precipitation that accumulation obtains for a long time again.
Alkane in the present invention refers to one or more the mixture in straight-chain paraffin or branched paraffin.
The dissolution process that alkane or paraffins mixture (hereinafter sometimes also referred to as " alkane ") dissolve long-chain biatomic acid generally operates at the temperature more than 110 DEG C, the temperature of heating for dissolving should be too not high yet, and general requirement is at least low 5 ~ 10 DEG C than solvent boiling point.For example solvent temperature can be 110 DEG C～200 DEG C, preferably 130 DEG C～180 DEG C, and more preferably 130 DEG C～160 DEG C.
Therefore, the boiling point of alkane is preferably more than 120 DEG C, is the highlyest generally no more than 350 DEG C, is preferably the scope of 150 DEG C～280 DEG C.
Easy to operate for crystallization processes, the fusing point of alkane solvent should be too not high, and general requirement is below 70 DEG C, realizes like this industrial being easy to.
The alkane that meets above requirement includes but not limited to: the mixture of one or more in octane, nonane, decane, undecane, dodecane, tridecane, the tetradecane, pentadecane, n-Hexadecane or heptadecane.
It should be appreciated by those skilled in the art that in above-mentioned alkane solvent and allow to contain a small amount of impurity, as a small amount of benzene class material or moisture etc., as long as this part impurity does not have a negative impact to follow-up recrystallizing technology.The alkane of the preferred purity of the present invention more than 95% is as recrystallization solvent.
Long-chain biatomic acid mixes with alkane, is heated to after certain temperature dissolving, clear liquid (being alkane solution) need to be separated.
The inventor is surprised to find that, adopt alkane to dissolve long-chain biatomic acid, the long-chain biatomic acid alkane solution color obtaining is very shallow, and the most of impurity containing in long-chain biatomic acid crude product is in dissolution process, substantially do not have dissolvedly, and then form color very dark precipitation.
General long-chain biatomic acid solvent crystallization process, comprises and uses acetic acid, ethanol equal solvent, long-chain biatomic acid and most of impurity are all dissolved in solvent, then carry out removal of impurities separation by the process of crystallization.Compared with conventional solvent crystallization technique, the outstanding feature of this technique is, alkane solvent can selectively remove most impurity dissolving the long-chain biatomic acid stage, and the alkane solution that dissolves long-chain biatomic acid is of light color, and foreign matter content is very low.When this also makes to use alkane solvent to dissolve long-chain biatomic acid, substantially need not add gac or only add the gac of minute quantity, just can reach and decolorizing effect like other solvent phase of use.Meanwhile, alkane solvent can recycle, and does not affect the color of long-chain biatomic acid crystallization.
In the time that alkane dissolves long-chain biatomic acid crude product, there is no dissolved impurity, need to, before crystallization, separate with alkane solution.The means that separate can be topple over, centrifugal, filtration etc., also can add and filter after a small amount of activated carbon decolorizing or centrifugal and obtain clear liquid, also can add a small amount of flocculating aids to filter as diatomite etc.
If add gac, the add-on of gac is relevant with the foreign matter content in long-chain biatomic acid crude product.
Because of alkane to the dissolving power of impurity a little less than, so clear phase color is very shallow in the alkane lysate of long-chain biatomic acid crude product, only need a small amount of gac just can reach the effect of decolouring.With respect to using other solvent, as acetic acid, ethanol etc., when long-chain biatomic acid adopts alkane as recrystallization solvent, the usage quantity of gac can significantly reduce, and generally can save more than 50% gac, has reduced production cost, has avoided environmental pollution.
If long-chain biatomic acid crude product is from the crystalline mother solution of producing in long-chain biatomic acid technique, as obtained after crystalline mother solution evaporate to dryness, or the throw out of long-chain biatomic acid sewage treatment plant, because their impurity and pigment content are high especially, be difficult to obtain qualified long-chain biatomic acid product by general technique.In conventional technique, can use gac to decolour to the long-chain biatomic acid mixture solution of difficulty decolouring, the usage quantity of gac is the amount with respect to long-chain biatomic acid up to 50% ~ 120%(), unstable product quality.
In the present invention, adopt this part long-chain biatomic acid mixture of alkane art breading, gac usage quantity can significantly reduce, and generally can obtain desirable effect as long as use with respect to 1 ~ 20% gac of long-chain biatomic acid amount.Certainly, industrial is that certain special application is considered, with respect to the amount of long-chain biatomic acid, also can use more than 20% gac, as 40% gac decolours.
To the long-chain biatomic acid alkane solution of isolated clarification, decrease temperature crystalline or separate out, obtains long-chain biatomic acid product.
The mode of long-chain biatomic acid alkane solution cooling, can adopt at ambient temperature cooling naturally, also can reduce temperature by temperature programmed control.Generally speaking, the slow cooling of temperature programmed control, beneficial to the crystallization of long-chain biatomic acid, crystallization rule and purity are high.
The terminal of cooling has no particular limits, and it is relevant with the temperature of the concrete alkane kind using, dissolving.Generally, the terminal of cooling can be 10 DEG C～80 DEG C, for example, drop to normal temperature (approximately 25 DEG C).After cooling, obtain long-chain biatomic acid solid, solid-liquid separation can obtain long-chain biatomic acid product.That suitable solid-liquid separating method includes but not limited to is centrifugal, filtration etc.
For the residual alkane on long-chain biatomic acid solid, can remove by conventional meanses such as cold water washing, easy volatile solvent washing, high temperature evaporations, then dry and obtain product.
Separate the alkane mother liquor after long-chain biatomic acid, do not need distillation purifying solvent, and can directly apply to crystallisation process next time, or be applied to crystallisation process next time after simple washing.In some cases, if alkane is repeatedly after crystallisation cycle, because of the accumulation of impurity in alkane solution, need to distill removal of impurities to alkane, then be applied to solvent crystallization process next time.Above-mentioned circulation can repeatedly, worsen until quality product is remarkable.
The inventor also finds, while adopting alkane as recrystallization solvent, separate out after long-chain biatomic acid product, in the alkane crystalline mother solution of gained, foreign matter content is very low, do not need distillation purifying solvent, and can directly apply to sepn process next time, this circulation can repeatedly, worsen until quality product is remarkable.This can significantly reduce the energy consumption in production, and significantly improves the crystallization yield of diprotic acid.
It needs to be noted, with respect to other solvents, alkane is a kind of chemically not too active compound, does not participate in chemical reaction under general condition.Therefore, adopt alkane to carry out crystallization and also there is following special advantage, obtain after long-chain biatomic acid solid in crystallization, in product residual a small amount of alkane solvent on downstream client's use almost without any impact.And using other solvents, as acetic acid, vinyl acetic monomer or ethanol, during as the recrystallization solvent of long-chain biatomic acid, the dissolvent residual in product, to different downstream clients, as nylon or polyester client, causes very large puzzlement.
Inventor's discovery, alkane is also particularly suitable for the treating process of the long-chain biatomic acid that foreign matter content is high.As the long-chain biatomic acid mixture obtaining after crystalline mother solution evaporation drying in acetic acid extraction long-chain biatomic acid process, this mixture contains a large amount of impurity bringing from fermented liquid, comprise the impurity such as albumen, sugar, organic pigment, this mixture uses the dissolving crystallized technique of alkane, can produce beyond thought refining effect.
The inventor also finds, alkane can directly contact with the crude product long-chain biatomic acid precipitation in fermented liquid, after dissolving long-chain biatomic acid, separates with fermented liquid system.Water insoluble because of alkane, be difficult for emulsifiedly simultaneously, the alkane solution that is dissolved with long-chain biatomic acid can obtain good separation with fermented liquid.Therefore, the long-chain biatomic acid crude product in the present invention can also be the direct acid precipitation gained of long-chain biatomic acid fermented liquid of Biological preparation; Or the long-chain biatomic acid crude product in the present invention can also be the long-chain biatomic acid fermented liquid of Biological preparation acid precipitation and obtaining again after activated carbon decolorizing, membrane filtration degerming.
In the time that alkane directly extracts the long-chain biatomic acid product in fermented liquid, add the order of mineral acid and alkane to have no particular limits, can adopt long-chain biatomic acid fermented liquid to add mineral acid acidifying, and then add the mode of alkane, also can adopt and first add alkane, and then add the mode of mineral acid acidifying.
Long-chain biatomic acid fermented liquid can be the fermented liquid of separating thallus not, can be also the clarified broth liquid obtaining through ceramic membrane filter.
After long-chain biatomic acid fermented liquid separates with alkane solution, its subsequent technique is with aforementioned consistent.
Embodiment
Below by embodiment, the present invention is described in detail, but the present invention is not limited to the embodiment listing herein.
In listed embodiment, use following testing method in this article:
1, diprotic acid gas chromatographic detection:
With reference to the mensuration of lipid acid in GB5413.27-2010 infant or baby food and dairy products.
2, ash content detects:
Get testing sample calcination in crucible, then calcination 2 hours in 700 ~ 800 DEG C of retort furnaces, gravimetry after cooling constant weight, calculates percent by weight.
3, determination of total nitrogen content:
Adopt Kjeldahl determination.
4, determination of light transmittance:
Diprotic acid sample dissolution is become to 5% sodium-salt aqueous solution, under room temperature, detect the transmittance at wavelength 430 nm places with UV.
Fermented liquid, the fermented liquid using in following examples crossed the preparation method of ceramic membrane clear liquid, fermented liquid centrifugal clear liquid can be referring to patent documentation 1.
embodiment 1
The tridecanyldicarboxylic acid fermented liquid of preparing according to the embodiment of patent documentation 15 methods.Be heated to 70 DEG C by vapor heat exchanger, then add alkali and regulate pH to 9.5, remove thalline by ceramic membrane filter, get tridecanyldicarboxylic acid film clear liquid 200 ml (212g), wherein diprotic acid content 160 g/L.Add sulfuric acid, regulate pH to 3, filter, dry, obtain tridecanyldicarboxylic acid crude product, yield is 96%.About 1400g n-tetradecane is added in tridecanyldicarboxylic acid crude product to insulated and stirred 1 hour in the oil bath of 150 DEG C.Then, add 0.3 gram of gac, insulated and stirred 1 hour in the oil bath of 150 DEG C.Insulation is filtered, isolating active charcoal, and the alkane solution obtaining is cooling naturally at room temperature, cools to after 50 DEG C, filters and obtains tridecanyldicarboxylic acid solid.30 milliliters of ethanol for this solid (10 DEG C) washing, dries, and obtains dicarboxylic acid product.Crystallization yield is 83%.Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
embodiment 2
The tridecanyldicarboxylic acid fermented liquid of preparing according to the embodiment of patent documentation 15 methods.Get tridecanyldicarboxylic acid fermented liquid 200 L (212kg), wherein diprotic acid content 162 g/L.About 2400kg n-tetradecane is added in tridecanyldicarboxylic acid fermented liquid, add sulfuric acid, regulate pH to 3, pressurize is warmed up to 120 DEG C, stirs 2 hours.Heat-insulation pressure keeping, leaves standstill after 2 hours separating thallus water.Remaining oil phase is warmed up to 140 DEG C, then, adds 0.3kg gac, insulated and stirred 1 hour at 140 DEG C.Insulation is filtered, isolating active charcoal, and the alkane solution obtaining is cooling naturally at room temperature, cools to after 50 DEG C, filters and obtains tridecanyldicarboxylic acid solid.30kg ethanol (20 DEG C) washing for this solid, dries, and obtains dicarboxylic acid product.Extract yield is 71%.Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
embodiment 3
The DC11 fermented liquid 200ml preparing according to the embodiment of patent documentation 13 methods, wherein diprotic acid content 120 g/L.Be heated to 40 DEG C by vapor heat exchanger, add sulfuric acid, regulate pH to 3, filter, dry, obtain DC11 crude product, yield is 93%.About 2200g nonane is added in DC11 crude product to insulated and stirred 2 hours in the oil bath of 140 DEG C.Then, add 0.4 gram of gac, insulated and stirred 1 hour in the oil bath of 140 DEG C.Insulation is filtered, isolating active charcoal, and the alkane solution obtaining is cooling naturally at room temperature, cools to after 30 DEG C, filters and obtains DC11 solid.30 milliliters of sherwood oils for this solid (30 DEG C) washing, dries, and obtains dicarboxylic acid product.Crystallization yield is 90%.Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
embodiment 4
The DC11 fermented liquid 170ml preparing according to the embodiment of patent documentation 13 methods, wherein diprotic acid content 120 g/L.Be heated to 40 DEG C by vapor heat exchanger, add sulfuric acid, regulate pH to 3, filter, dry, obtain DC11 crude product, yield is 92%.By the crystalline mother solution obtaining in the embodiment of the present invention 3, nonane solution adds in DC11 crude product, insulated and stirred 2 hours in the oil bath of 140 DEG C.Then, add 0.3 gram of gac, insulated and stirred 1 hour in the oil bath of 140 DEG C.Insulation is filtered, isolating active charcoal, and the alkane solution obtaining is cooling naturally at room temperature, cools to after 30 DEG C, filters and obtains DC11 solid.20 milliliters of sherwood oils for this solid (30 DEG C) washing, dries, and obtains dicarboxylic acid product.Crystallization yield is 98%.Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
embodiment 5
The SL-AH fermented liquid 300ml preparing according to the embodiment of patent documentation 14 methods, bactofugation body, obtains supernatant liquor 280ml, wherein diprotic acid content 168 g/L.Add sulfuric acid, regulate pH to 3, filter, dry, obtain SL-AH crude product.About 1500g n-heptadecane is added in SL-AH crude product to insulated and stirred 1 hour in the oil bath of 200 DEG C.Then, add 0.4 gram of gac, insulated and stirred 1 hour in the oil bath of 200 DEG C.Insulation is filtered, isolating active charcoal, and the alkane solution obtaining is cooling naturally at room temperature, cools to after 70 DEG C, filters and obtains SL-AH solid.30 milliliters of sherwood oils for this solid (30 DEG C) washing, dries, and obtains dicarboxylic acid product.Crystallization yield is 78%.Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
embodiment 6
The SL-AH fermented liquid 300ml preparing according to the embodiment of patent documentation 14 methods, bactofugation body, obtains supernatant liquor 250ml, wherein diprotic acid content 168 g/L.Add sulfuric acid, regulate pH to 3, filter, dry, obtain SL-AH crude product.The crystalline mother solution obtaining in embodiment 5 is added in SL-AH crude product to insulated and stirred 1 hour in the oil bath of 200 DEG C.Then, add 0.4 gram of gac, insulated and stirred 1 hour in the oil bath of 200 DEG C.Insulation is filtered, isolating active charcoal, and the alkane solution obtaining is cooling naturally at room temperature, cools to after 70 DEG C, filters and obtains SL-AH solid.30 milliliters of sherwood oils for this solid (30 DEG C) washing, dries, and obtains dicarboxylic acid product.Crystallization yield is 99%.Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
embodiment 7
The SL-AH fermented liquid 300ml preparing according to the embodiment of patent documentation 14 methods, bactofugation body, obtains supernatant liquor 250ml, wherein diprotic acid content 168 g/L.Add sulfuric acid, regulate pH to 3, filter, dry, obtain SL-AH crude product.The crystalline mother solution obtaining in embodiment 6 is added in SL-AH crude product to insulated and stirred 1 hour in the oil bath of 200 DEG C.Then, add 0.6 gram of gac, insulated and stirred 1 hour in the oil bath of 200 DEG C.Insulation is filtered, isolating active charcoal, and the alkane solution obtaining is cooling naturally at room temperature, cools to after 70 DEG C, filters and obtains SL-AH solid.30 milliliters of sherwood oils for this solid (30 DEG C) washing, dries, and obtains dicarboxylic acid product.Crystallization yield is 99%.Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
embodiment 8
9-alkene-DC18 fermented liquid 5000 ml that prepare according to the embodiment of patent documentation 12 methods, are heated to 70 DEG C by vapor heat exchanger, then add alkali and regulate pH to 11, remove thalline by ceramic membrane filter, obtain 9-alkene-DC18 film clear liquid.Get filtrate 600ml, wherein diprotic acid content 7.1%, adds sulfuric acid, regulates pH to 3, cools to 20 DEG C, filters, and dries, and obtains 9-alkene-DC18 crude product.About 2500g n-hexadecane and 2,3,3-trimethylpentane mixture (ratio 20:1) are added in 9-alkene-DC18 crude product to insulated and stirred 1 hour in the oil bath of 160 DEG C.Then, add 3 grams of diatomite, insulation is filtered, and separates diatomite, and the alkane solution obtaining is lowered the temperature in 10 DEG C of water-baths, cools to after 20 DEG C, filters and obtains 9-alkene-DC18 solid.This solid is pulverized, and then uses 30 milliliters of ethanol (10 DEG C) washing, and filtering drying, obtains dicarboxylic acid product.Crystallization yield is 87%.Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
embodiment 9
The 16-dicarboxylic acid fermented liquid of preparing according to the embodiment of patent documentation 18 methods.Be heated to 70 DEG C by vapor heat exchanger, then add alkali and regulate pH to 9.5, remove thalline by ceramic membrane filter, obtain 16-dicarboxylic acid film clear liquid.Get 500 ml film clear liquids, wherein diprotic acid content 106.2 g/L add sulfuric acid, regulate pH to 3, filter, and dry, and obtain 16-dicarboxylic acid crude product.About 2400g n-tridecane is added in 16-dicarboxylic acid crude product to insulated and stirred 1 hour in the oil bath of 170 DEG C.Then, add 0.5 gram of gac, insulated and stirred 1 hour in the oil bath of 170 DEG C.Insulation is filtered, isolating active charcoal, and the alkane solution obtaining, with 20 DEG C/h of programmed coolings, cools to after 50 DEG C, filters and obtains 16-dicarboxylic acid solid.30 milliliters of sherwood oils for this solid (20 DEG C) washing, dries, and obtains dicarboxylic acid product.Crystallization yield is 92%.Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
embodiment 10
The 16-dicarboxylic acid fermented liquid of preparing according to the embodiment of patent documentation 18 methods.Be heated to 70 DEG C by vapor heat exchanger, then add alkali and regulate pH to 9.5, remove thalline by ceramic membrane filter, obtain 16-dicarboxylic acid film clear liquid.Get 500 ml film clear liquids, wherein diprotic acid content 106.2 g/L add sulfuric acid, regulate pH to 3, filter, and dry, and obtain 16-dicarboxylic acid crude product.The crystalline mother solution of embodiment 9 is added in 16-dicarboxylic acid crude product to insulated and stirred 1 hour in the oil bath of 170 DEG C.Then, add 0.5 gram of gac, insulated and stirred 1 hour in the oil bath of 170 DEG C.Insulation is filtered, isolating active charcoal, and the alkane solution obtaining, with 20 DEG C/h of programmed coolings, cools to after 50 DEG C, filters and obtains 16-dicarboxylic acid solid.30 milliliters of sherwood oils for this solid (20 DEG C) washing, dries, and obtains dicarboxylic acid product.Crystallization yield is 97%.Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
embodiment 11
According to the method for the embodiment of patent documentation 1 30, SL-AH crude product is operated, obtain acetic acid primary crystallization mother liquor.By 950 grams of acetic acid crystalline mother solution evaporations, obtain, after wet solid, continuing the dry 24 grams of diprotic acid crude products that obtain.Measuring its content consists of: containing 60% SL-AH (DC12), 13% DC14 (DC14), other diprotic acid and monoprotic acid 19%.About 1500g decane is added in diprotic acid crude product to insulated and stirred 1 hour in the oil bath of 160 DEG C.Then, add 0.5 gram of gac, insulated and stirred 1 hour in the oil bath of 160 DEG C.Insulation is filtered, isolating active charcoal, and the alkane solution obtaining is cooling naturally at room temperature, cools to after 50 DEG C, filters to obtain hybrid long chain dicarboxylic acid solid.30 milliliters of sherwood oils for this solid (30 DEG C) washing, dries, and obtains mixed dibasic acid product.Crystallization yield is 75% (with respect to crude product).Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
embodiment 12
According to the method for the embodiment of patent documentation 1 27, SL-AH crude product is operated, obtain butylacetate primary crystallization crystalline mother solution.By 500 grams of butylacetate crystalline mother solution evaporations, obtain, after wet solid, continuing the dry 6 grams of diprotic acid crude products that obtain.Measuring its content consists of: containing 50% DC12,18% DC14, other diprotic acid and monoprotic acid 21%.About 500g dodecane is added in diprotic acid crude product to insulated and stirred 1 hour in the oil bath of 160 DEG C.Then, add 0.2 gram of gac, insulated and stirred 1 hour in the oil bath of 160 DEG C.Insulation is filtered, isolating active charcoal, and the alkane solution obtaining is cooling naturally at room temperature, cools to after 50 DEG C, filters to obtain hybrid long chain dicarboxylic acid solid.10 milliliters of sherwood oils for this solid (30 DEG C) washing, dries, and obtains mixed dibasic acid product.Crystallization yield is 72% (with respect to crude product).Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
embodiment 13
According to the method for the embodiment of patent documentation 1 27, SL-AH crude product is operated, obtain butylacetate primary crystallization crystalline mother solution.By 500 grams of butylacetate crystalline mother solution evaporations, obtain, after wet solid, continuing the dry 6 grams of diprotic acid crude products that obtain.Measuring its content consists of: containing 50% DC12,18% DC14, other diprotic acid and monoprotic acid 21%.Crystalline mother solution in embodiment 12 is added in diprotic acid crude product to insulated and stirred 1 hour in the oil bath of 160 DEG C.Then, add 0.3 gram of gac, insulated and stirred 1 hour in the oil bath of 160 DEG C.Insulation is filtered, isolating active charcoal, and the alkane solution obtaining is cooling naturally at room temperature, cools to after 50 DEG C, filters to obtain hybrid long chain dicarboxylic acid solid.10 milliliters of sherwood oils for this solid (30 DEG C) washing, dries, and obtains mixed dibasic acid product.Crystallization yield is 94% (with respect to crude product).Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
embodiment 14
According to the method for the embodiment of patent documentation 1 26, SL-AH crude product is operated, obtain ethyl acetate primary crystallization mother liquor.By 1200 grams of ethyl acetate crystalline mother solution evaporations, obtain, after wet solid, continuing the dry 10 grams of diprotic acid crude products that obtain.Measuring its content consists of: containing 55% DC12,12% DC14, other diprotic acid and monoprotic acid 19%.About 400g kerosene (containing 4% aromatic hydrocarbon substance) is added in diprotic acid crude product, insulated and stirred 1 hour in the oil bath of 110 DEG C, diprotic acid does not all dissolve.Then, add 0.2 gram of gac, insulated and stirred 1 hour in the oil bath of 110 DEG C.Insulation is filtered, isolating active charcoal and undissolved diprotic acid and impurity thereof, and the alkane solution obtaining is cooling naturally at room temperature, cools to after 40 DEG C, filters to obtain hybrid long chain dicarboxylic acid solid.The alkane mother liquor that separation is obtained joins in undissolved diprotic acid and Mixture of Activated Carbon, and insulated and stirred 1 hour in the oil bath of 110 DEG C repeats described filtering for crystallizing process above, obtains long-chain biatomic acid solid.Repeat again above-mentioned mother liquor operation secondary, diprotic acid residual in crude product is dissolved complete.
All long-chain biatomic acid solids that obtain are merged, and 20 milliliters of sherwood oils for solid (30 DEG C) washing, dries, and obtains mixed dibasic acid product.Crystallization yield is 89% (with respect to crude product).Products obtained therefrom is carried out to diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
table 1
Can be clear and definite by above embodiment, in process for purification of the present invention, by using alkane as recrystallization solvent, thereby gac usage quantity is low or can not use gac, and, alkane crystalline mother solution can directly apply to without distillation purifying next sepn process, thereby significantly reduces production energy consumption, and significantly improves the crystallization yield of long-chain biatomic acid.
Claims (14)
1. a process for purification for long-chain biatomic acid, the method comprises the following steps:
1) long-chain biatomic acid crude product and alkane Hybrid Heating are dissolved;
2) isolate alkane solution; And
3) decrease temperature crystalline or separate out and obtain long-chain biatomic acid product.
2. a process for purification for long-chain biatomic acid, the method comprises the following steps:
1) long-chain biatomic acid crude product and alkane Hybrid Heating are dissolved;
2) isolate alkane solution;
3) decrease temperature crystalline or separate out and obtain long-chain biatomic acid product; And
4) utilize above-mentioned steps 3) in the crystalline mother solution that obtains as alkane solvent, repeat above step 1) to 3), obtain other long-chain biatomic acid product.
3. the process for purification of long-chain biatomic acid according to claim 1 and 2, wherein, the long-chain biatomic acid fermentation broth extract that described long-chain biatomic acid crude product is Biological preparation.
4. the process for purification of long-chain biatomic acid according to claim 3, wherein, described long-chain biatomic acid crude product obtains as follows: the direct acid precipitation of long-chain biatomic acid fermented liquid of described Biological preparation is also isolated; The long-chain biatomic acid fermented liquid of described Biological preparation acid precipitation being isolated again after activated carbon decolorizing, membrane filtration degerming; Or, after the direct acid precipitation of long-chain biatomic acid fermented liquid of described Biological preparation separation, then obtain after washing or high-temperature water processing.
5. the process for purification of long-chain biatomic acid according to claim 1 and 2, wherein, described long-chain biatomic acid crude product is the by product obtaining in long-chain biatomic acid extraction or solvent crystallization process.
6. the process for purification of long-chain biatomic acid according to claim 5, wherein, the source of described long-chain biatomic acid crude product is: the long-chain biatomic acid precipitation of long-chain biatomic acid sewage treatment plant; Or, the long-chain biatomic acid mixture obtaining after long-chain biatomic acid recrystallization mother liquor is dry.
7. the process for purification of long-chain biatomic acid according to claim 1 and 2, wherein, described long-chain biatomic acid crude product obtains as follows: the direct acid precipitation of long-chain biatomic acid fermented liquid of described Biological preparation obtains; Or the long-chain biatomic acid fermented liquid of described Biological preparation acid precipitation and obtaining again after activated carbon decolorizing, membrane filtration degerming.
8. the process for purification of long-chain biatomic acid according to claim 1 and 2, wherein, the main component of described long-chain biatomic acid crude product is one or more the mixture in nonane diacid, sebacic acid, DC11, SL-AH, tridecanyldicarboxylic acid, DC14,15 carbon dicarboxylic acids, 16-dicarboxylic acid, DC17, DC18 or 9-alkene-18 carbon diacid.
9. the process for purification of long-chain biatomic acid according to claim 1 and 2, wherein, described alkane is one or more the mixture in straight-chain paraffin or branched paraffin.
10. the process for purification of long-chain biatomic acid according to claim 9, wherein, the boiling point of described alkane is the scope of 120 DEG C～350 DEG C, and fusing point is below 70 DEG C.
The process for purification of 11. long-chain biatomic acids according to claim 8, wherein, described alkane is one or more the mixture in octane, nonane, decane, undecane, dodecane, tridecane, the tetradecane, pentadecane, n-Hexadecane or heptadecane.
The process for purification of 12. long-chain biatomic acids according to claim 1 and 2, wherein, step 1) in solvent temperature be 110～200 DEG C and lower than 5～10 DEG C of the boiling points of alkane or mixed alkanes.
The process for purification of 13. long-chain biatomic acids according to claim 1 and 2, wherein, step 2) in by toppling over, method centrifugal or that filter obtains alkane solution.
The process for purification of 14. long-chain biatomic acids according to claim 1 and 2, wherein, in step 1) long-chain biatomic acid crude product dissolve completely after, add activated carbon decolorizing, then obtain alkane solution.
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| CN114685269B (en) * | 2020-12-29 | 2024-05-03 | 上海凯赛生物技术股份有限公司 | Purification method of long-chain dibasic acid and long-chain dibasic acid product |
| CN113773192A (en) * | 2021-08-25 | 2021-12-10 | 史兰东 | Method for purifying dodecyl dicarboxylic acid by using mixed extraction agent |
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