CN116550283A - Compound decolorizing agent for decolorizing dicarboxylic acid fermentation liquor and method for decolorizing and refining dicarboxylic acid fermentation liquor - Google Patents
Compound decolorizing agent for decolorizing dicarboxylic acid fermentation liquor and method for decolorizing and refining dicarboxylic acid fermentation liquor Download PDFInfo
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- CN116550283A CN116550283A CN202210110934.5A CN202210110934A CN116550283A CN 116550283 A CN116550283 A CN 116550283A CN 202210110934 A CN202210110934 A CN 202210110934A CN 116550283 A CN116550283 A CN 116550283A
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000855 fermentation Methods 0.000 title claims abstract description 47
- 230000004151 fermentation Effects 0.000 title claims abstract description 47
- 150000001875 compounds Chemical class 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 16
- 238000007670 refining Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 160
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 35
- 238000001914 filtration Methods 0.000 claims abstract description 33
- 239000004927 clay Substances 0.000 claims abstract description 21
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 14
- 238000004042 decolorization Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000012065 filter cake Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 77
- 239000000706 filtrate Substances 0.000 claims description 39
- 239000011148 porous material Substances 0.000 claims description 38
- 239000007787 solid Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 abstract description 20
- 239000000049 pigment Substances 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000001953 recrystallisation Methods 0.000 abstract description 4
- 239000002932 luster Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 239000012535 impurity Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 6
- 241001052560 Thallis Species 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000002207 metabolite Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RZUDZAJRBFRQLS-UHFFFAOYSA-N 2-dodecylpropanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)C(O)=O RZUDZAJRBFRQLS-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- -1 organic acid compound acids Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D36/00—Filter circuits or combinations of filters with other separating devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention provides a compound decolorizer for decolorizing a dicarboxylic acid fermentation broth and a method for decolorizing and refining the dicarboxylic acid fermentation broth, wherein the compound decolorizer comprises the following components in parts by weight: 4-6 parts of activated carbon, 3-5 parts of activated clay and 3-5 parts of montmorillonite. The compound decoloring agent is used for the adsorption decoloring of a solution containing the dicarboxylic acid salt, and the decoloring solution containing the dicarboxylic acid salt is obtained after solid-liquid separation. Further adding acid into the decolouring liquid of the dicarboxylic acid salt to perform neutralization reaction, converting the dicarboxylic acid salt into dicarboxylic acid and completely separating out the dicarboxylic acid from the aqueous solution, and filtering to obtain a dicarboxylic acid filter cake with low chromaticity; and (3) refining and extracting the dicarboxylic acid from the dicarboxylic acid filter cake to obtain the polymer-grade long-chain dicarboxylic acid. Compared with the decolorizer which only uses one component, the invention can obtain more satisfactory decolorization effect, so that the dicarboxylic acid and pigment are separated more thoroughly, the product has white color and luster and more practical application value, and the product meeting the polymerization requirement can be easily obtained by adopting solvent recrystallization refining in the follow-up process.
Description
Technical Field
The invention relates to a dicarboxylic acid refining technology, in particular to a decoloring process in a dicarboxylic acid refining process.
Background
The dicarboxylic acid produced by fermentation is a metabolite produced by microorganisms using carbon sources such as alkane or fatty acid. The molecular general formula is C n H 2n-2 O 4 Wherein n is 8-18, and dicarboxylic acid contains two terminal carboxyl groups, and is a monomer raw material for synthesizing engineering plastics, hot melt adhesives and the like.
The quality of the polymer monomer is the key of project achievement industrialization, restricts the application of the polymer monomer in the downstream field, and is a common key problem to be solved by the industry. The removal of trace pigments and other impurities in the product is a difficult problem for technological workers.
Dicarboxylic acid is a metabolite of microbial fermentation, the composition of fermentation liquor is complex, wherein pigment components are the most complex, various pigments such as polarity, non-polarity, water solubility, fat solubility and the like are contained, the pigment content and the pigment type are continuously changed along with treatment conditions, and great technical challenges are brought to obtaining a product with white appearance.
In the existing technology adopted in the dicarboxylic acid industry, pigment is mainly removed in the solvent recrystallization refining process of dicarboxylic acid. The post-treatment of the dicarboxylic acid product comprises two processes, namely, the fermentation broth is acidified to obtain a crude dicarboxylic acid product, the extraction process is carried out in a water phase, the crude dicarboxylic acid is dissolved in a solvent, the solvent is recrystallized and refined, active carbon is firstly added for decolorization and filtration, and then the decolorized filtrate is crystallized, so that the dicarboxylic acid product is finally obtained. It is known that the removal of pigment impurities in the aqueous phase of the dicarboxylic acid extraction stage provides a cost advantage over removal in solvents. The decolorization effect of the decolorizer in water is superior to that in the solvent phase due to the strong polarity of water. Although activated carbon and other materials are selected to be used as the decoloring agent in the industry, due to the variety and the types of the decoloring agent, proper and effective adsorbents and decoloring conditions are not selected, and the problem of low decoloring and impurity removing efficiency exists.
Disclosure of Invention
Aiming at the defects, the invention provides a compound decolorizer for decolorizing a dicarboxylic acid fermentation broth and a corresponding decolorization method, which have obviously improved decolorization effect compared with the prior art by adopting an adsorbent.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the technical purpose of the first aspect of the invention is to provide a compound decolorizer for decolorizing a dicarboxylic acid fermentation broth, which comprises the following components in parts by weight:
4-6 parts of active carbon
3-5 parts of activated clay
3-5 parts of montmorillonite.
Further, in one embodiment of the present invention, the activated carbon is graded by using activated carbon with different pore diameters, and comprises, based on 100% of the total weight of the activated carbon:
10% -20% of microporous active carbon with aperture of 1-3 nm
50% -80% of mesoporous activated carbon with pore diameter of 3-50 nm
10% -30% of macroporous active carbon with the pore diameter larger than 50 nm.
The technical purpose of the second aspect of the invention is to provide a method for decoloring dicarboxylic acid fermentation broth, which comprises the steps of adding the compound decoloring agent into a solution containing dicarboxylic acid salt, performing adsorption decoloring, and removing the compound decoloring agent through solid-liquid separation to obtain a decoloring solution containing dicarboxylic acid salt;
wherein, the compound decolorizer comprises the following components in parts by weight:
4-6 parts of active carbon
3-5 parts of activated clay
3-5 parts of montmorillonite.
Further, the dosage of the compound decolorizer is 0.5-100 g/L fermentation liquor, preferably 1-30 g/L fermentation liquor according to the volume of the fermentation liquor.
Further, the activated carbon in the compound decolorizer adopts activated carbon with different pore diameters for grading, and the activated carbon is taken as 100% of the total weight of the activated carbon, and the compound decolorizer comprises:
10% -20% of microporous active carbon with aperture of 1-3 nm
50% -80% of mesoporous activated carbon with pore diameter of 3-50 nm
10% -30% of macroporous active carbon with the pore diameter larger than 50 nm.
Further, the adsorption temperature is 10-100 ℃, preferably 20-60 ℃. The adsorption time is 30-60 min.
Further, the solid-liquid separation adopts a graded filtration mode, firstly, active carbon, activated clay and montmorillonite are removed by filtration through a filter material with the aperture of 1-50 mu m, a first-stage filtrate is obtained, and then, the rest solid is removed through a filter material with the aperture of 0.2-1 mu m, so that a clear and colorless second-stage filtrate is obtained.
The technical object of the third aspect of the present invention is to provide a method for refining dicarboxylic acid by fermentation, comprising the following steps:
performing solid-liquid separation on the fermentation liquor to obtain clear filtrate containing the dicarboxylic acid salt, adding a compound decolorizer into the clear filtrate to perform adsorption decolorization, and filtering to obtain a decolorized solution of the dicarboxylic acid salt; adding acid into the decolouring liquid of the dicarboxylic acid salt to perform neutralization reaction, converting the dicarboxylic acid salt into dicarboxylic acid and completely separating out the dicarboxylic acid from the aqueous solution, and filtering to obtain a dicarboxylic acid filter cake with low chromaticity; refining and extracting dicarboxylic acid from the dicarboxylic acid filter cake to obtain polymer-grade long-chain dicarboxylic acid;
wherein, the compound decolorizer comprises the following components in parts by weight:
4-6 parts of active carbon
3-5 parts of activated clay
3-5 parts of montmorillonite.
Further, the dosage of the compound decolorizer is 0.5-100 g/L fermentation liquor, preferably 1-30 g/L fermentation liquor according to the volume of the fermentation liquor.
Further, the activated carbon in the compound decolorizer adopts activated carbon with different pore diameters for grading, and the activated carbon is taken as 100% of the total weight of the activated carbon, and the compound decolorizer comprises:
10% -20% of microporous active carbon with aperture of 1-3 nm
50% -80% of mesoporous activated carbon with pore diameter of 3-50 nm
10% -30% of macroporous active carbon with the pore diameter larger than 50 nm.
Further, the adsorption temperature is 10-100 ℃, preferably 20-60 ℃. The adsorption time is 30-60 min.
Further, adding a compound decoloring agent for decoloring, filtering in a grading filtering mode, filtering by adopting a filter material with the aperture of 1-50 mu m to remove active carbon, activated clay and montmorillonite to obtain a first-stage filtrate, and removing residual solids by using a filter material with the aperture of 0.2-1 mu m to obtain a clear and colorless second-stage filtrate.
Further, the dicarboxylic acid cake is purified and extracted by solvent recrystallization, which is a method known in the art.
Further, the fermentation broth is a metabolite obtained by microbial fermentation, wherein the dicarboxylic acid has a molecular formula of C n H 2n-2 O 4 Wherein n is 8-18, and the fermentation liquor contains a single dicarboxylic acid or mixed dicarboxylic acid.
Further, the fermentation broth is subjected to solid-liquid separation by means including, but not limited to, flocculation sedimentation, microfiltration, ultrafiltration, centrifugation, pressure filtration, vacuum filtration, etc., to obtain a clarified dicarboxylate solution.
Further, the acidification is performed by methods well known in the art. Specifically, the pH value of the acidification is 2.0-4.0. The acid used for acidification is H in any concentration 2 SO 4 、HNO 3 HCl or H 3 PO 4 Inorganic or organic acids such as formic acid, acetic acid, propionic acid, etc., clean acids or recovered acids, single acids or inorganic and organic acid compound acids can be selected.
Embodiments of the invention have the following advantages:
(1) In the dicarboxylic acid refining process, the decoloring process is indispensable, but the research of the prior art is often not important, but the inventor discovers that the decoloring effect directly influences whether the product meets the related requirements. The inventor finds that only one component of decolorizing agent, such as active carbon or active clay, cannot obtain satisfactory decolorizing effect, and obtains a compound decolorizing agent through research, which can decolorize dicarboxylic acid fermentation liquor, so that dicarboxylic acid and pigment are more thoroughly separated, the product has white color and luster and more practical application value, and the product meeting the polymerization requirement can be easily obtained by adopting solvent recrystallization refining.
(2) The inventor further researches and discovers that compared with the method which only uses active carbon with single aperture, the method further adopts active carbon grading with different apertures, can better improve the decolorization effect, and after the active carbon with different apertures is compounded with active clay and montmorillonite, small-molecule and macromolecular pigments can be adsorbed, weak-polarity and polar pigments can be adsorbed, water-soluble and oil-soluble pigments can be adsorbed, and compared with the prior art, the method adopts a single adsorbent, the efficiency of adsorbing and removing pigments is higher, and the color of the dicarboxylic acid decolorization filtrate is lighter.
(3) The method adopts the mode of grading the activated carbon with different pore diameters, activated clay and montmorillonite to decolor, thereby effectively reducing the use amount of the activated carbon, and obtaining a satisfactory decoloring effect compared with the method of decoloring by singly using the activated carbon.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
The following examples illustrate the purification of dicarboxylic acids by fermentation, wherein the decolorization filtrate and the color of the product are measured using the method of GB 3143-1982.
Example 1
I. 100L fermentation broth containing decadicarboxylic acid is filtered to remove solid impurities such as thalli and the like, and clear filtrate is obtained.
II. 150g of compound decolorizer is added into the dicarboxylate filtrate, the dicarboxylate filtrate is adsorbed and treated for 60min at 50 ℃, and the clarified dicarboxylate decolorized solution is obtained through two-stage filtration.
And III, adding sulfuric acid into the dicarboxylic acid salt decolorized solution, adjusting the pH value to 4.0, heating to 95 ℃, cooling to room temperature, filtering, washing and drying to obtain the decadicarboxylic acid.
Wherein, the compound decolorizer comprises the following components in parts by weight:
4 parts of active carbon, namely a mixture of water and water,
3.5 parts of activated clay
3.5 parts of montmorillonite.
The active carbon adopts active carbon with different pore diameters for grading, and the active carbon is prepared from the following active carbon in percentage by weight of 100 percent:
10% of microporous active carbon with the aperture of 1-3 nm,
70% of mesoporous activated carbon with the aperture of 3-50 nm,
and the pore diameter of the macroporous active carbon is more than 20 percent of that of 50 nm.
The color of the dicarboxylic acid salt decolorized solution obtained in II and the color of the deca-dicarboxylic acid product obtained in III are shown in Table 1.
Example 2
I. 100L of fermentation broth containing undecanedicarboxylic acid was filtered to remove solid impurities such as bacterial cells, and a clear filtrate was obtained.
II. 300g of compound decolorizer is added into the dicarboxylate filtrate, the dicarboxylate filtrate is adsorbed and treated for 60min at 60 ℃, and the clarified dicarboxylate decolorized solution is obtained through two-stage filtration.
And III, adding sulfuric acid into the dicarboxylic acid salt decolorized solution, adjusting the pH value to 4.0, heating to 95 ℃, cooling to room temperature, filtering, washing and drying to obtain the undecanedicarboxylic acid.
Wherein, the compound decolorizer comprises the following components in parts by weight:
4 parts of active carbon, namely a mixture of water and water,
4 parts of activated clay,
4 parts of montmorillonite.
The active carbon adopts active carbon with different pore diameters for grading, and the active carbon is prepared from the following active carbon in percentage by weight of 100 percent:
15% of microporous active carbon with the aperture of 1-3 nm,
70% of mesoporous activated carbon with the aperture of 3-50 nm,
and 15% of macroporous active carbon with the pore diameter of more than 50 nm.
The color of the dicarboxylic acid salt decolorized solution obtained in II and the undecanedicarboxylic acid product obtained in III are shown in Table 1.
Example 3
I. 100L fermentation broth containing dodecanedicarboxylic acid is filtered to remove solid impurities such as bacteria and the like, and clear filtrate is obtained.
II. 600g of compound decolorizing agent is added into the dicarboxylate filtrate, the dicarboxylate filtrate is adsorbed and treated for 60min at 60 ℃, and the clarified dicarboxylate decolorized solution is obtained through two-stage filtration.
And III, adding sulfuric acid into the dicarboxylic acid salt decolorized solution, adjusting the pH value to 4.0, heating to 95 ℃, cooling to room temperature, filtering, washing and drying to obtain the dodecanedicarboxylic acid.
Wherein, the compound decolorizer comprises the following components in parts by weight:
4.5 parts of active carbon, and the like,
4 parts of activated clay,
3 parts of montmorillonite.
The active carbon adopts active carbon with different pore diameters for grading, and the active carbon is prepared from the following active carbon in percentage by weight of 100 percent:
20% of microporous active carbon with the aperture of 1-3 nm,
65% of mesoporous activated carbon with the aperture of 3-50 nm,
and 15% of macroporous active carbon with the pore diameter of more than 50 nm.
The chromaticity of the dicarboxylic acid product obtained in II and III is shown in the table.
Example 4
I. 100L fermentation broth containing tridecanedicarboxylic acid is filtered, and solid impurities such as thalli and the like are removed, so that clear filtrate is obtained.
II. 900g of compound decolorizer is added into the dicarboxylate filtrate, the dicarboxylate filtrate is adsorbed and treated for 60min at 60 ℃, and the clarified dicarboxylate decolorized solution is obtained through two-stage filtration.
And III, adding sulfuric acid into the dicarboxylic acid salt decolorized solution, adjusting the pH value to 4.0, heating to 95 ℃, cooling to room temperature, filtering, washing and drying to obtain the tridecyl dicarboxylic acid.
Wherein, the compound decolorizer comprises the following components in parts by weight:
4.5 parts of active carbon, and the like,
4 parts of activated clay,
4 parts of montmorillonite.
The active carbon adopts active carbon with different pore diameters for grading, and the active carbon is prepared from the following active carbon in percentage by weight of 100 percent:
15% of microporous active carbon with the aperture of 1-3 nm,
60% of mesoporous activated carbon with the aperture of 3-50 nm,
and the pore diameter of the macroporous active carbon is greater than 25 percent of that of 50 nm.
The color of the dicarboxylic acid salt decolorized solution obtained in II and the color of the tridecanedicarboxylic acid product obtained in III are shown in Table 1.
Example 5
I. 100L fermentation broth containing tetradecadicarboxylic acid is filtered to remove solid impurities such as thalli and the like, and clear filtrate is obtained.
II. Adding 1200g of compound decolorizing agent into the dicarboxylate filtrate, performing adsorption treatment at 60 ℃ for 60min, and performing two-stage filtration to obtain clarified dicarboxylate decolorizing solution.
And III, adding sulfuric acid into the dicarboxylic acid salt decolorized solution, adjusting the pH value to 4.0, heating to 95 ℃, cooling to room temperature, filtering, washing and drying to obtain the tetradecanedicarboxylic acid.
Wherein, the compound decolorizer comprises the following components in parts by weight:
5 parts of active carbon, namely, the mixture of the active carbon and the water,
4.5 parts of activated clay,
4.5 parts of montmorillonite.
The active carbon adopts active carbon with different pore diameters for grading, and the active carbon is prepared from the following active carbon in percentage by weight of 100 percent:
20% of microporous active carbon with the aperture of 1-3 nm,
50% of mesoporous activated carbon with the aperture of 3-50 nm,
the pore diameter of the macroporous active carbon is more than 30 percent of that of the macroporous active carbon with the pore diameter of more than 50 nm.
The color of the dicarboxylic acid salt decolorized solution obtained in II and the color of the tetradecanedicarboxylic acid product obtained in III are shown in Table 1.
Example 6
I. 100L fermentation broth containing pentadecadicarboxylic acid is filtered to remove solid impurities such as thalli and the like, and clear filtrate is obtained.
II. 1500g of compound decolorizer is added into the dicarboxylate filtrate, the dicarboxylate filtrate is adsorbed at 60 ℃ for 60min, and the clarified dicarboxylate decolorized solution is obtained through two-stage filtration.
And III, adding sulfuric acid into the dicarboxylic acid salt decolorized solution, adjusting the pH value to 4.0, heating to 95 ℃, cooling to room temperature, filtering, washing and drying to obtain pentadecadicarboxylic acid.
Wherein, the compound decolorizer comprises the following components in parts by weight:
5.5 parts of active carbon, and the like,
5 parts of activated clay,
5 parts of montmorillonite.
The active carbon adopts active carbon with different pore diameters for grading, and the active carbon is prepared from the following active carbon in percentage by weight of 100 percent:
20% of microporous active carbon with the aperture of 1-3 nm,
60% of mesoporous activated carbon with the aperture of 3-50 nm,
and the pore diameter of the macroporous active carbon is more than 20 percent of that of 50 nm.
The color of the dicarboxylic acid salt decolorized solution obtained in II and the color of the pentadecade dicarboxylic acid product obtained in III are shown in Table 1.
Example 7
I. 100L fermentation broth containing hexadecanedicarboxylic acid is filtered to remove solid impurities such as thalli and the like, and clear filtrate is obtained.
II. 1800g of compound decolorizer is added into the dicarboxylate filtrate, the dicarboxylate filtrate is adsorbed and treated for 60min at 60 ℃, and the clarified dicarboxylate decolorized solution is obtained through two-stage filtration.
And III, adding sulfuric acid into the dicarboxylic acid salt decolorized solution, adjusting the pH value to 4.0, heating to 95 ℃, cooling to room temperature, filtering, washing and drying to obtain hexadecanedicarboxylic acid.
Wherein, the compound decolorizer comprises the following components in parts by weight:
6 parts of active carbon, namely a mixture of the active carbon and the water,
5 parts of activated clay,
5 parts of montmorillonite.
The active carbon adopts active carbon with different pore diameters for grading, and the active carbon is prepared from the following active carbon in percentage by weight of 100 percent:
20% of microporous active carbon with the aperture of 1-3 nm,
60% of mesoporous activated carbon with the aperture of 3-50 nm,
and the pore diameter of the macroporous active carbon is more than 20 percent of that of 50 nm.
The color of the dicarboxylic acid salt decolorized solution obtained in II and the hexadecane dicarboxylic acid product obtained in III are shown in Table 1.
Comparative example 1
I. 100L fermentation broth containing dodecanedicarboxylic acid is filtered to remove solid impurities such as bacteria and the like, and clear filtrate is obtained.
II. 600g of activated carbon is added into the dicarboxylate filtrate, adsorption treatment is carried out for 60min at 60 ℃, and the two-stage filtration is carried out to obtain clarified dicarboxylate decolorization solution.
And III, adding sulfuric acid into the dicarboxylic acid salt decolorized solution, adjusting the pH value to 4.0, heating to 95 ℃, cooling to room temperature, filtering, washing and drying to obtain the dodecanedicarboxylic acid.
The color of the dicarboxylic acid salt decolorized solution obtained in II and the color of the dodecadicarboxylic acid product obtained in III are shown in Table 1.
Comparative example 2
I. 100L fermentation liquor containing the dodecanedicarboxylic acid is filtered, and solid impurities such as thalli and the like are removed, so that clear fermentation filtrate is obtained.
II. 1800g of active carbon is added into the dicarboxylic acid salt filtrate, the absorption treatment is carried out for 60min at 60 ℃, and the clear dicarboxylic acid salt decolorized solution is obtained through two-stage filtration.
And III, adding sulfuric acid into the dicarboxylic acid salt decolorized solution, adjusting the pH value to 4.0, heating to 95 ℃, cooling to room temperature, filtering, washing and drying to obtain the dodecanedicarboxylic acid.
The color of the dicarboxylic acid salt decolorized solution obtained in II and the color of the dodecadicarboxylic acid product obtained in III are shown in Table 1.
Table 1.
Claims (12)
1. The compound decoloring agent for decoloring the dicarboxylic acid fermentation broth is characterized by comprising the following components in parts by weight:
4-6 parts of active carbon
3-5 parts of activated clay
3-5 parts of montmorillonite.
2. The compound decolorizer according to claim 1, wherein the activated carbon is graded by using activated carbon with different pore diameters, based on 100% of the total weight of the activated carbon, and comprises:
10% -20% of microporous active carbon with aperture of 1-3 nm
50% -80% of mesoporous activated carbon with pore diameter of 3-50 nm
10% -30% of macroporous active carbon with the pore diameter larger than 50 nm.
3. The method for decoloring the dicarboxylic acid fermentation broth is characterized in that the compound decoloring agent is added into a solution containing dicarboxylic acid salt, adsorption decoloring is carried out, and the compound decoloring agent is removed by solid-liquid separation to obtain a decoloring solution containing dicarboxylic acid salt;
wherein, the compound decolorizer comprises the following components in parts by weight:
4-6 parts of active carbon
3-5 parts of activated clay
3-5 parts of montmorillonite.
4. A method according to claim 3, characterized in that the amount of the compound decolorizing agent is 0.5-100 g/L of fermentation broth, preferably 1-30 g/L of fermentation broth, based on the volume of fermentation broth.
5. The method according to claim 3, wherein the activated carbon in the compound decolorizer is graded by activated carbon with different pore diameters, based on 100% of the total weight of the activated carbon, comprising:
10% -20% of microporous active carbon with aperture of 1-3 nm
50% -80% of mesoporous activated carbon with pore diameter of 3-50 nm
10% -30% of macroporous active carbon with the pore diameter larger than 50 nm.
6. The method of claim 3, wherein the temperature of adsorption is 10-100 ℃.
7. The method of claim 3, wherein the solid-liquid separation is performed by a fractional filtration method, wherein activated carbon, activated clay and montmorillonite are removed by filtration with a filter material with a pore diameter of 1-50 μm to obtain a first-stage filtrate, and the remaining solids are removed by a filter material with a pore diameter of 0.2-1 μm to obtain a clear and colorless second-stage filtrate.
8. A method for refining dicarboxylic acid by fermentation, comprising the following steps:
performing solid-liquid separation on the fermentation liquor to obtain clear filtrate containing the dicarboxylic acid salt, adding a compound decolorizer into the clear filtrate to perform adsorption decolorization, and filtering to obtain a decolorized solution of the dicarboxylic acid salt; adding acid into the decolouring liquid of the dicarboxylic acid salt to perform neutralization reaction, converting the dicarboxylic acid salt into dicarboxylic acid and completely separating out the dicarboxylic acid from the aqueous solution, and filtering to obtain a dicarboxylic acid filter cake with low chromaticity; refining and extracting dicarboxylic acid from the dicarboxylic acid filter cake to obtain polymer-grade long-chain dicarboxylic acid;
wherein, the compound decolorizer comprises the following components in parts by weight:
4-6 parts of active carbon
3-5 parts of activated clay
3-5 parts of montmorillonite.
9. The method according to claim 8, characterized in that the amount of the compound decolorizer is 0.5-100 g/L of fermentation broth, preferably 1-30 g/L of fermentation broth, based on the volume of the fermentation broth.
10. The method of claim 8, wherein the activated carbon in the compound decolorizer is graded with activated carbon of different pore sizes, based on 100% total weight of activated carbon, comprising:
10% -20% of microporous active carbon with aperture of 1-3 nm
50% -80% of mesoporous activated carbon with pore diameter of 3-50 nm
10% -30% of macroporous active carbon with the pore diameter larger than 50 nm.
11. The method of claim 8, wherein the temperature of adsorption is 10-100 ℃ and the time of adsorption is 30-60 min.
12. The method of claim 8, wherein the filtering is performed by a step filtration method after adding the compound decolorizer for decolorization, wherein the activated carbon, the activated clay and the montmorillonite are removed by a filter material with a pore diameter of 1-50 μm to obtain a first-stage filtrate, and the rest solid is removed by a filter material with a pore diameter of 0.2-1 μm to obtain a clear and colorless second-stage filtrate.
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