CN112206748B - Preparation method of efficient composite adsorbent for refining pentadecade diacid - Google Patents
Preparation method of efficient composite adsorbent for refining pentadecade diacid Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
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Abstract
The invention discloses a preparation method of a high-efficiency composite adsorbent for refining pentadecade diacid, which comprises the steps of reacting chitosan in dilute acetic acid solution for 1-3 h at normal temperature, adding pretreated activated carbon and methacrylic acid, uniformly mixing, and N 2 And (3) reacting under protection, adding potassium persulfate, continuing the reaction, and filtering, washing and drying after the reaction is finished to obtain the composite adsorbent. The surface area of the composite adsorbent prepared by the invention can exceed 1000m 2 G (BET), the adsorption efficiency is ensured; the average pore diameter is 2.1nm (BJH), which is a mesoporous adsorbent, is favorable for macromolecular substances to enter the adsorbent, and is easy to analyze substances after adsorption saturation in a solvent; the adsorbent is used for purifying pentadecade diacid, and can fully ensure that the chromaticity and the total nitrogen content reach the standards; the adsorbent is easy to desorb after being adsorbed and saturated, can be repeatedly used for many times, and is more environment-friendly.
Description
Technical Field
The invention belongs to the field of pentadecade diacid product refining, and particularly relates to a preparation method of a high-efficiency composite adsorbent for refining pentadecade diacid.
Background
Pentadecanoic acid is an important raw material for synthesizing the rare fragrances cyclopentadecanone and 3-methyl cyclopentadecanone (musk ketone) and long-chain nylon. Pentadecanoic acid does not exist in nature, at present, normal alkane is mainly converted into pentadecanoic acid through a microorganism specific reaction, and the process has the advantages of simple route, high yield and low cost, and is industrially applied; however, in the actual industrial production process, the fermentation process research of pentadecade dibasic acid is mature, but the fermentation liquid is a complex multiphase system which contains unreacted normal alkane, microorganism, culture medium, metabolite and the like. Even though the product is treated, the product often contains a large amount of impurities such as protein, pigment and the like, the purity and the appearance quality of the product are seriously affected, and the value of the product is greatly affected. Therefore, the refining process becomes an important link for restricting the development of pentadecade dibasic acid.
The main method for removing impurities and decoloring the pentadecade diacid at present comprises the following steps: aqueous phase method, solvent method, esterification method. The aqueous phase method mainly comprises the steps of adding a decolorizing agent, pH acidification crystallization and the like into an aqueous solution, and has the advantages of simple operation, low cost and small environmental load, but the product quality is generally poor due to the lack of an efficient adsorbent. The solvent method is to purify by using a solvent recrystallization method, and the method has the advantages of complex operation, high investment, difficult process control, large dosage of organic solvent, serious solvent loss and great improvement of production cost. The esterification method is to make acid and low-carbon alcohol undergo the process of esterification reaction, then make saponification and hydrolysis so as to obtain the refined binary acid.
Patent CN 105712871A provides a method for purifying long chain dibasic acids, which comprises: pretreating long-chain dibasic acid termination fermentation liquor, acidizing, treating by concentrated sulfuric acid, adding active carbon to adsorb impurities, cooling to separate out long-chain dibasic acid crystals, filtering, washing and drying to obtain long-chain dibasic acid. Although the method can obtain purer long-chain dibasic acid, the method has poor effect because an efficient adsorbent is not adopted.
Chinese patent CN105582901a discloses a preparation of an adsorbent for long carbon chain diacid fermentation broth, adding comonomer 1, 3-pentadiene-1-carboxylic acid, diallyl maleate, 4-vinylpyridine-butyl acrylate, ethylene Glycol Dimethacrylate (EGDMA) into methyl acrylate polymerization to generate a polymer with long carbon chain alkyl and diacid functional groups on the skeleton, which is used for extracting decolored long carbon chain diacid, and has the advantages of high adsorption capacity and capability of reducing the loss of diacid caused by repeated crystallization and filtration. However, the preparation of the adsorbent of the invention requires the use of multiple comonomers and is relatively costly.
Chinese patent CN106902732a discloses a composite adsorbent for removing peculiar smell component in beet sugar, which is formed by compounding activated carbon and filter aid or by compounding activated carbon, resin and filter aid. The composite adsorbent overcomes the defect of weak polar molecule adsorption capacity of common activated carbon, and has more excellent peculiar smell removal effect.
Chinese patent CN107597066a discloses an activated carbon/chitosan composite adsorbent for removing humic acid from water.
At present, a high-efficiency composite adsorbent is not available for purifying and refining long carbon chain dibasic acid.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the invention provides a preparation method of an efficient composite adsorbent for refining pentadecade diacid, and the adsorbent prepared by the method has the characteristics of high treatment efficiency, capability of simultaneously completing impurity removal and decoloration and repeated utilization for a plurality of times.
The technical scheme is as follows: the aim of the invention is achieved by the following technical scheme:
the invention provides a preparation method of a high-efficiency composite adsorbent for refining pentadecade diacid, which couples the advantages of pure natural material activated carbon and chitosan, not only can provide large specific surface area, but also fully utilizes the functional group of the chitosan, and comprises the following steps:
(1) Pretreatment of activated carbon:
adding active carbon into HNO with mass fraction of 20-30% 3 Soaking in the solution at 40-60 deg.c for 8-12 hr; washing the impregnated activated carbon to be neutral, and drying for 10-20 h at 100-120 ℃; so as to achieve the purpose of fully pore-forming.
(2) Preparation of composite adsorbent:
chitosan is reacted in dilute acetic acid solution for 1 to 3 hours at normal temperature, the pretreated activated carbon in the step (1) is added, methacrylic acid is added, and after uniform mixing, the chitosan is added in N at 50 to 100 DEG C 2 Reacting for 0.5-2 h under protection, adding potassium persulfate, continuing to react for 1-3 h, filtering, washing and drying after the reaction is finished to obtain the composite adsorptionAnd (3) an agent. The chitosan and the dilute acetic acid are prepared into a solution, the activated carbon is crosslinked with the chitosan, and the methacrylic acid and the potassium persulfate regulate and control the performance of the adsorbent.
Preferably, the surface area of the composite adsorbent is 1040-1100 m 2 /g (BET), average pore diameter is 2.1nm (BJH).
Preferably, the activated carbon is one or two of walnut shell activated carbon and coconut shell activated carbon, and preferably the composite adsorbent prepared by crosslinking the activated carbon and chitosan has the best decoloring and nitrogen removing effects.
Preferably, in the step (1), 15 to 25ml of HNO is added per 1g of activated carbon 3 In solution.
Preferably, in the step (2), the mass fraction of the diluted acetic acid solution is 1-4%, and each 1g of chitosan is reacted with 20-40 ml of the diluted acetic acid solution.
Preferably, in the step (2), the mass ratio of chitosan to activated carbon is 1:2-1:6.
Preferably, in the step (2), the mass ratio of the methacrylic acid to the activated carbon is 1:5-1:10.
Preferably, in the step (2), the mass of potassium persulfate is 1 to 3% of the mass of methacrylic acid.
Preferably, in the step (2), the washing is performed in the following manner: repeatedly washing with acetic acid solution with mass fraction of 0.5-2%, ethanol and distilled water for 3-5 times. And washing in the washing mode, and removing unreacted chitosan, methacrylic acid and potassium persulfate through full washing.
Preferably, the activated carbon in step (1) is prepared by the steps of:
(1) Taking active carbon precursor, drying, cooling to room temperature, adding the active carbon precursor into the mixture with the mass fraction of 50-80% H 3 PO 4 Stirring the solution fully, reacting for 10-20 h at 40-60 ℃ under sealed condition, and drying for 10-20 h at 100-120 ℃ for later use;
(2) At N 2 Under the protection, heating the dried active carbon precursor to carbonization temperature, reacting for 1-2 h, heating to activation temperature, and preserving heat for 2-10 h; at N 2 Cooling to room temperature under protectionActivating materials;
(3) Adding the activating material into an HCl solution with the mass fraction of 0.5-2%, wherein the mass of the HCl solution is 8-12 times that of the activating material, and stirring or vibrating for 2-4 hours for pickling; washing with water to neutrality at 70-90 deg.c and drying at 100-120 deg.c for 10-20 hr to obtain active carbon. The obtained activated carbon has large specific surface area and good crosslinking effect with chitosan.
In order to make the activated carbon have better performance, it is further preferable that in the step (2), the heating rate of the activated precursor is 5-20 ℃/min, the carbonization temperature is 200-300 ℃, and the activation temperature is 400-550 ℃.
The beneficial effects are that:
the carrier active carbon has high specific surface area, and the composite adsorbent provided by the invention adopts natural material chitosan and coconut shell or walnut shell as raw materials, and has the advantages of low cost, no pollution and easiness in degradation. The surface area of the composite adsorbent prepared may exceed 1000m 2 G (BET), the adsorption efficiency is ensured; the average pore diameter is 2.1nm (BJH), which is a mesoporous adsorbent, is favorable for macromolecular substances to enter the adsorbent, and is easy to analyze substances after adsorption saturation in a solvent; the adsorbent is used for purifying pentadecade diacid, and can fully ensure that the chromaticity and the total nitrogen content reach the standards. The decoloring rate (ultraviolet-visible spectrophotometer) is up to 85% -96%; the total nitrogen content can be reduced from 378ppm to 20-35 ppm, the adsorbent is easy to desorb after being saturated in adsorption, and the adsorbent can be reused for multiple times, and the partially deactivated adsorbent can be easily degraded due to the good biodegradability of the composite adsorbent, so that the composite adsorbent is more environment-friendly.
Detailed Description
The technical scheme of the present invention is described in detail below through specific examples, but the scope of the present invention is not limited to the examples.
Example 1
(1) 100g of granular coconut shell of active carbon precursor is taken, dried, cooled to room temperature, added into 400ml of H with mass fraction of 80% 3 PO 4 The solution is fully stirred, reacted for 10 hours at 50 ℃ under sealed condition, and dried for 10 hours at 120 ℃ for standby.
(2) Putting the dried precursor into a tube furnace, and adding the precursor into N 2 Under protection, heating to 300 ℃ at a heating rate of 5 ℃/min for reaction for 1h, then heating to 550 ℃, and preserving heat for 2h, then adding the catalyst into N 2 The protection was lowered to room temperature to give 42.5g of an activated material.
(3) The activated material was placed in a vessel, 500g of 0.5% HCl solution by mass was added thereto, and stirred for 4 hours for pickling. Then washing with deionized water to neutrality at 70deg.C, and drying at 100deg.C for 20 hr to obtain 41.3g of active carbon.
(4) Adding 1000ml of 20% HNO into the obtained active carbon 3 Immersing in the solution at 60 ℃ for 12h. The impregnated activated carbon is washed to be neutral by deionized water and then dried for 20 hours at 100 ℃.
(5) Adding 5g of chitosan into 200ml of 1% mass fraction dilute acetic acid solution, reacting at normal temperature for 3h, adding 30g of treated activated carbon, adding 3g of methacrylic acid, mixing uniformly, and adding the mixture into N at 100 DEG C 2 Reacting for 0.5h under protection, weighing 0.03g of potassium persulfate, continuing to react for 3h, filtering after the reaction is finished, repeatedly washing for 5 times by adopting 0.5% acetic acid solution, ethanol and distilled water, and vacuum drying for 12h at 60 ℃. 34.5g of high-efficiency composite adsorbent can be obtained, and the surface area is 1095m 2 /g (BET), average pore diameter is 2.1nm (BJH).
10g of the high-efficiency composite adsorbent prepared by the method is added into 3L of pentadecadiacid (with the mass concentration of 4%) fermentation broth, the mixture is stirred for 3 hours at the temperature of 30 ℃, and after filtration, the decoloring rate of the solution is up to 98.1%, and the total nitrogen content is reduced from 378ppm to 20ppm.
Example 2
(1) Taking 100g of granular walnut shell of active carbon precursor, drying, cooling to room temperature, adding 800ml of H with mass fraction of 50% 3 PO 4 The solution is fully stirred, reacted for 20 hours at 50 ℃ under sealed condition, and dried for 20 hours at 100 ℃ for standby.
(2) Putting the dried precursor into a tube furnace, and adding the precursor into N 2 Under protection, heating to 200 ℃ at a heating rate of 20 ℃/min for 2h, then heating to 400 ℃, preserving heat for 10h, and then adding the catalyst into N 2 The protection was lowered to room temperature to give 45.7g of an activator.
(3) The activating material is placed in a container, 400g of HCl solution with the mass fraction of 2% is added, and the mixture is vibrated for 2 hours for pickling. Then, the mixture was washed with deionized water at 70℃to neutrality and dried at 120℃for 10 hours to give 44.6g of activated carbon.
(4) The resulting activated carbon was added to 700ml of 30% HNO 3 Immersing in the solution at 60 ℃ for 12h. The impregnated activated carbon is washed to be neutral by deionized water and then dried for 10 hours at 120 ℃.
(5) Adding 5g of chitosan into 100ml of 4% diluted acetic acid solution, reacting at normal temperature for 1h, adding 10g of treated activated carbon, adding 2g of methacrylic acid, mixing uniformly, and adding the mixture into N at 50 DEG C 2 Reacting for 2h under protection, weighing 0.06g of potassium persulfate, continuing to react for 3h, filtering after the reaction is finished, repeatedly washing for 5 times by adopting 2% acetic acid solution, ethanol and distilled water, and vacuum drying for 12h at 60 ℃. 14.8g of high-efficiency composite adsorbent can be obtained, and the surface area is 1074m 2 /g (BET), average pore diameter is 2.1nm (BJH).
10g of the high-efficiency adsorbent prepared by the method is added into 3L of pentadecadiacid crude (the mass concentration is 4%) fermentation liquor, the mixture is stirred for 3 hours at 30 ℃, the decolorization rate of the solution is up to 95.3% after filtration, and the total nitrogen content is reduced from 378ppm to 22ppm.
Example 3
(1) Taking 100g of granular walnut shell of active carbon precursor, drying, cooling to room temperature, adding 600ml of 65% H by mass 3 PO 4 The solution is fully stirred, reacted for 15 hours at 50 ℃ under sealed condition, and dried for 15 hours at 100 ℃ for standby.
(2) Putting the dried precursor into a tube furnace, and adding the precursor into N 2 Under protection, heating to 250 ℃ at a heating rate of 10 ℃/min for reaction for 1.5h, then heating to 500 ℃, and preserving heat for 10h, then adding the catalyst into the reaction mixture, and finally adding the catalyst into the reaction mixture 2 The protection was lowered to room temperature to give 44.2g of an activated material.
(3) The activating material is placed in a container, 450g of HCl solution with the mass fraction of 1% is added, and the mixture is vibrated for 2 hours for pickling. Then washing with deionized water to neutrality at 70deg.C, and drying at 110deg.C for 15h to obtain 43.5g of active carbon.
(4) Adding the obtained activated carbon into 900mlHNO with 25% fraction 3 Immersing in the solution at 60 ℃ for 12h. The impregnated activated carbon is washed to be neutral by deionized water and then dried for 15 hours at 120 ℃.
(5) Adding 5g of chitosan into 150ml of 2% diluted acetic acid solution, reacting at normal temperature for 1h, adding 15g of treated activated carbon, adding 2g of methacrylic acid, mixing uniformly, and adding the mixture into N at 80 DEG C 2 Reacting for 1.5h under protection, weighing 0.03g of potassium persulfate, continuing to react for 3h, filtering after the reaction is finished, repeatedly washing for 5 times by adopting 1.5% acetic acid solution, ethanol and distilled water, and vacuum drying for 12h at 60 ℃. Thus obtaining 19.2g of high-efficiency composite adsorbent with the surface area of 1052m 2 /g (BET), average pore diameter is 2.1nm (BJH).
10g of the high-efficiency adsorbent prepared by the method is added into 3L of pentadecadiacid crude (the mass concentration is 4%) fermentation liquor, the mixture is stirred for 3 hours at 30 ℃, the decolorization rate of the solution is up to 92.3% after filtration, and the total nitrogen content is reduced from 378ppm to 25ppm.
Example 4
Filtering the high-efficiency composite adsorbent subjected to adsorption saturation in the embodiment 2, drying in vacuum at 70 ℃ for 12 hours, repeatedly washing with absolute ethyl alcohol for 5 times at normal temperature, and drying in vacuum at 60 ℃ for 24 hours to obtain the regenerated adsorbent.
10g of regenerated high-efficiency adsorbent is added into 3L of pentadecadiacid crude (with the mass concentration of 4%) fermentation liquor, the mixture is stirred for 3 hours at the temperature of 30 ℃, and after filtration, the decoloring rate of the solution is up to 94.2%, and the total nitrogen content is reduced from 378ppm to 26ppm.
The high-efficiency adsorbent regenerated for 5 times has a decoloring rate of 86.7% and a total nitrogen content of 34.5ppm.
The surface area of the composite adsorbent prepared by the invention can exceed 1000m 2 G (BET), the adsorption efficiency is ensured; the average pore diameter is 2.1nm (BJH), which is a mesoporous adsorbent, is favorable for macromolecular substances to enter the adsorbent, and is easy to analyze substances after adsorption saturation in a solvent; the adsorbent is used for purifying pentadecade diacid, and can fully ensure that the chromaticity and the total nitrogen content reach the standards. The decoloring rate (ultraviolet-visible spectrophotometer) is up to 85% -96%; the total nitrogen content can be reduced from 378ppm to 20-35 ppm. Adsorption and desorption of adsorbent after saturationIs easy to recycle for many times, and is more environment-friendly.
As described above, although the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limiting the invention itself. Various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The preparation method of the efficient composite adsorbent for refining pentadecade diacid is characterized by comprising the following steps of:
(1) Pretreatment of activated carbon:
adding 20-30% of HNO (HNO) into the activated carbon 3 Immersing in the solution at 40-60 ℃ for 8-12 h; washing the impregnated activated carbon to be neutral, and drying at 100-120 ℃ for 10-20 hours;
(2) Preparation of composite adsorbent:
reacting chitosan in dilute acetic acid solution for 1-3 h at normal temperature, adding the pretreated activated carbon in the step (1), adding methacrylic acid, uniformly mixing, and then adding the mixture in N at 50-100 DEG C 2 Reacting for 0.5-2 h under protection, adding potassium persulfate, continuing to react for 1-3 h, filtering, washing and drying after the reaction is finished, so as to obtain the composite adsorbent;
the mass ratio of the methacrylic acid to the activated carbon is 1:5-1:10.
2. The method for preparing a high-efficiency composite adsorbent for refining pentadecade diacid according to claim 1, wherein the activated carbon is one or two of walnut shell activated carbon and coconut shell activated carbon.
3. The method for producing a high-efficiency composite adsorbent for purification of pentadecade diacid according to claim 1, wherein in the step (1), 15 to 25ml of HNO is added per 1g of activated carbon 3 In solution.
4. The method for preparing the efficient composite adsorbent for refining pentadecade diacid according to claim 1, wherein in the step (2), the mass fraction of the dilute acetic acid solution is 1-4%, and each 1g of chitosan reacts with 20-40 ml of the dilute acetic acid solution.
5. The method for preparing the efficient composite adsorbent for refining pentadecade diacid according to claim 1, wherein in the step (2), the mass ratio of chitosan to activated carbon is 1:2-1:6.
6. The method for preparing a high-efficiency composite adsorbent for refining pentadecade diacid according to claim 1, wherein in the step (2), the mass of potassium persulfate is 1-3% of the mass of methacrylic acid.
7. The method for preparing the efficient composite adsorbent for refining pentadecade diacid according to claim 1, wherein in the step (2), the washing mode is as follows: repeatedly washing with acetic acid solution with the mass fraction of 0.5-2%, ethanol and distilled water for 3-5 times.
8. The method for preparing a high-efficiency composite adsorbent for refining pentadecade diacid according to claim 1, wherein the activated carbon in step (1) is prepared by the steps of:
(1) Taking an active carbon precursor, drying, cooling to room temperature, and adding the active carbon precursor into the mixture with the mass fraction of 50-80% H 3 PO 4 Fully stirring the solution, reacting for 10-20 hours at 40-60 ℃ under a sealed condition, and drying for 10-20 hours at 100-120 ℃ for later use;
(2) At N 2 Under the protection, heating the dried active carbon precursor to carbonization temperature, reacting for 1-2 h, heating to activation temperature, and preserving heat for 2-10 h; at N 2 The temperature is reduced to room temperature under protection to obtain an activated material;
(3) Adding the activating material into an HCl solution with the mass fraction of 0.5-2%, wherein the mass of the HCl solution is 8-12 times that of the activating material, and stirring or vibrating for 2-4 hours for pickling; washing with water to neutrality at 70-90 ℃, and drying for 10-20 h at 100-120 ℃ to obtain the activated carbon.
9. The method for preparing a high-efficiency composite adsorbent for refining pentadecade diacid according to claim 8, wherein in the step (2), the heating rate of the active precursor is 5-20 ℃/min, the carbonization temperature is 200-300 ℃, and the activation temperature is 400-550 ℃.
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| WO2016143217A1 (en) * | 2015-03-11 | 2016-09-15 | 花王株式会社 | Thin paper |
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| EP2158034A1 (en) * | 2007-05-01 | 2010-03-03 | Norit Nederland B.V. | Composite adsorbent material |
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