CN103877945A - Preparation method of biological binary composite adsorbent in glycerol triacetate refinement process - Google Patents
Preparation method of biological binary composite adsorbent in glycerol triacetate refinement process Download PDFInfo
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- CN103877945A CN103877945A CN201410135865.9A CN201410135865A CN103877945A CN 103877945 A CN103877945 A CN 103877945A CN 201410135865 A CN201410135865 A CN 201410135865A CN 103877945 A CN103877945 A CN 103877945A
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Abstract
The invention provides a preparation method of a biological binary composite adsorbent in a glycerol triacetate refinement process, and aims at overcoming the deficiencies of relatively poor selectivity, easiness in saturation, non-ideal subsequent refinement effect, high use cost and the like due to adoption of single active carbon as an adsorbent for removing residual organic matters in a subsequent process of glycerol triacetate in the prior art. According to the method, the surface of active carbon is grafted and coated with cyclodextrin, so that the content of oxygen-containing groups on the surface of active carbon is increased, the characteristics of active carbon are added, and active carbon can form an inclusion compound and a molecular assembly system together with a large quantity of organic and inorganic molecules under the Van der Waals' force, the hydrophobic interaction force, the effect of matching between molecules of subjective and objective bodies and the like; the enveloping effect of selective combination is commonly known as the molecular identification, and finally a high-efficiency elution effect is achieved.
Description
Technical field
The present invention relates to the ester class purifying field in organic chemistry, be specifically related to the preparation method of the adsorbent using in triacetyl glycerine production technology.
Background technology
The industry such as plasticizer, polyalcohol has been put into effect relevant limit standard from 2007, require to strengthen plasticizer the organic detection of micro-low concentration and control in polyalcohol.This pressure standard remains organic compounds and heavy metal as negative index using what affect its quality purity in plasticizer, polyalcohol, and national structure will regularly inspect by random samples.Coherent detection standard major part is directly quoted food service industry examination criteria method, and tobacco business is by conventional filter stick plasticizer, and triacetyl glycerine is as one of Typical Representative of controlling.
Find according to the organic compound research to residual low concentration in triacetyl glycerine product, it mainly comes from raw material and production process, glyceryl triacetate is by glycerine, acetic acid, under the effect of acidic catalyst, heating obtains semi-finished product with dehydrating agent, through decolouring, depickling, refining forming, conventional band aqua has benzene, toluene, the ester classes such as ethyl acetate, and cyclohexane, raw acetic acid itself just contains formic acid, propionic acid, ethanol, acetaldehyde etc., at the temperature of 100 ℃ of left and right, react, so can contain large weight organic compounds remains in semi-finished product, through distillation refining after, also may there is the composition that affects its quality safety in glyceryl triacetate.
In prior art, the active carbons that adopt adsorb the residual organic matter of low concentration in triacetyl glycerine more, although active carbon has good absorption elution, but the absorption of Active Carbon in Organic is a surface process, selectively poor, easily saturated, and, the micropore prosperity of active carbon, so that some macromolecular compound cannot enter micropore, in the time of practical application, need to select different activated carbon varieties, increase cost, and the effect that single-activity charcoal is removed residual low-concentration organic in product for current elution is not very good, cannot meet the renewal of national industry, higher, tighter standard-required.
For making all internal control limit indexs of existing triacetyl glycerine product reach the requirement of the limit value of tobacco business completely, realize more fully quality lifting of glycerol triacetate for tobacco, effectively control VOC residual concentration in triacetyl glycerine; Research and develop the residual organic matter that low concentration in triacetyl glycerine is removed in a kind of efficiently elution, have close ester, the biological eluent of novel class of close alcohol becomes plasticizer industry development and existence, the important topic that must attract great attention.
Cyclodextrin is to form cyclic oligosaccharide by glucose unit with alpha-1, 4-glucosidic key joint.The molecular structure of cyclodextrin is comparatively special, and its outer surface has hydrophily, and inside is a hydrophobic cavity with certain size, and this makes cyclodextrin possess the peculiar property of " outer hydrophilic, interior hydrophobic ".This special structure can make the cyclodextrin can the many guest molecules of envelope, as inorganic compound, organic compound, rare gas etc.Due to the unique envelope ability of cyclodextrin inner chamber to guest molecule, it has been widely used in the fields such as molecular recognition, adsorbing separation, medicament slow release and inductor.For example Multifunctional palygorskite base adsorbing material-201110122456.1, it makes carrier with palygorskite, and the compound of sucrose, beta-schardinger dextrin-, shitosan is that carbon source, six ferrous sulfate hydrate ammoniums are catalyst, adopt roasting direct legal system for obtaining.Experimental results show that, this composite has the ability of efficient removal organic matter, heavy metal ion, color and stink simultaneously, therefore, having very large application potential processing aspect the waste water such as toxic organic compound, heavy metal ion and dyestuff.
This patented technology is for sewage disposal, and the application belongs to ester class purifying, and the technical problem of the two technical field and solution is different.Above-mentioned patent is using the stronger material of absorption property as carrier, by cyclodextrin and sucrose, chitosan loaded on this carrier, loading on cyclodextrin on palygorskite etc. is as carbon source, to after its carbonization, load on palygorskite surface with amorphous carbon, make palygorskite surface contain C-H organo-functional group, make composite there is certain close Organic, the raw material and the preparation technology's relative complex that use, be difficult to control, and the know-why of this patent is that palygorskite surface polarity is changed, site alive to nonpolar phenol molecule increases, therefore Pyrogentisinic Acid's adsorption capacity and clearance have been improved, and residual organic matter is mainly Ester in triacetyl glycerine, sorbing material described in this patent does not have good compatibility for the Ester being mingled in triacetyl glycerine, cannot be applicable in the follow-up process for refining of triacetyl glycerine.
In sum, remove at present the residual lower organic adsorbent of concentration in triacetyl glycerine product and have a lot of problems, adopt nontoxic, harmless raw material, nontoxic, under harmless and normal condition, use, selectively high, eco-friendly new bio eluent is significant to the sustainable development of plasticizer industry.
Summary of the invention
In order to solve the problem existing in background technology, overcome single-activity charcoal as removing selectively poor, easy undesirable, the high deficiency of use cost of saturated, follow-up refining effect of residual organic matter adsorbent in triacetyl glycerine subsequent technique, the object of the present invention is to provide the preparation method of biological binary compound adsorbent in a kind of triacetyl glycerine process for refining, reach efficient elution effect.
For achieving the above object, the present invention is by the following technical solutions:
The preparation method of biological binary compound adsorbent in triacetyl glycerine process for refining, adopts cyclodextrin, water and active carbon as raw material, is prepared according to following steps:
A, with weight ratio calculate, take cyclodextrin and water according to the ratio of cyclodextrin: water=0.04～0.60:1;
B, Jiang Shui put into the container that band stirs, and add thermal agitation, in the time that temperature reaches and keep 45-50 ℃, divide four equivalent to add cyclodextrin, keep temperature, control mixing speed 60r/min, treat that cyclodextrin all adds, and is fully uniformly mixed;
C, by the cyclodextrin solution heating preparing, temperature remains on 70-80 ℃, keeps 10min to make cyclodextrin hydrate;
D, calculate with weight ratio, according to active carbon: cyclodextrin hydrate=0.05～0.1:1, take and active carbon is added in cyclodextrin hydrate, after stirring, be heated to 90 ℃, stir and keep 60 minutes;
E, stop heating and stir, by mixture take out, be placed in baking oven, be heated to 110 ℃ of oven dry, control moisture lower than 2%;
F, by dry after mixture take out, in hothouse, be cooled to normal temperature, pulverize, sieve, control granularity obtain biological binary compound adsorbent at 200-300 order.
Described active carbon form is any one of granular activated carbon, cylindrical active carbon, spherical activated charcoal.
Described active carbon kind is any one of cocoanut active charcoal, active fruit shell carbon.
Described cyclodextrin is any one of a-cyclodextrin, beta-schardinger dextrin-and gamma-cyclodextrin.
The present invention is coated by activated carbon surface being carried out to grafting with cyclodextrin, improve the content of activated carbon surface oxy radical, analyze with thermogravimetric analysis and can draw by FT-IR, infrared spectrum curve and thermogravimetric curve all can prove the existence of cyclodextrin, this just shows that cyclodextrin has successfully been grafted to activated carbon surface, increase active carbon characteristic, make it can be according to Van der Waals force, hydrophobic interaction power, the intermolecular matching effect of Subjective and Objective etc. and many organic and inorganic molecule formation inclusion compound and molecular assembly systems, the envelope effect of this selective combination is usually said molecular recognition, consequently form Subjective and Objective inclusion complex due to solubility and the inclusion ability of cyclodextrin in water, the physicochemical property that has simultaneously changed active carbon and cyclodextrin reaches efficient elution effect.
Apply this product, can make triacetyl glycerine product reach at present the limit value requirement to residual low concentration organic matter standard regulation in product both at home and abroad, meet the renewal constantly proposing, higher, stricter requirement.
Adopt by active carbon and cyclodextrin binary laminating production adsorbent, contrast single active carbon and there is clear superiority with other for the refining sorbing material of the follow-up operation of triacetyl glycerine:
A, because active carbon and cyclodextrin belong to natural biological goods, China is the big country that produces two kinds of products, the enterprise of this product of domestic production is a lot of at present, aboundresources, for the active carbon of the production cyclodextrin of living, because consumption is few, resource and have in price very large space.
The natural degradation of b, this adsorbent is functional, and iterative regenerable utilizes 10-15 time, and consumption is few, can not produce secondary pollution, belongs to Green Product.
C, this adsorbent consumption are few, and molecular surface contains abundant polar group and molecular recognition material, and stability and reusability are respond well.
D, this adsorbent raw materials belong to natural products, completely in GB/2760 prescribed limit, with NF standard, there is relevant authoritative technical standard support, have cocksure security, selected raw material are the qualified products with country and industry standard, and production process only need to be selected to order according to production technology and technical indicator, the process equipment of researching and developing by oneself carries out follow-up optimizing machining technology can be produced, and material cost and processing production equipment technique are simple.
E, this adsorbent have reusable, and energy consumption is low, fairly obvious to residual low-concentration organic removal effect in the follow-up subtractive process of triacetyl glycerine, can effectively improve for manufacturing enterprise the quality of product, meet the demand for development of national green environmental protection and economy.
The employing single-activity charcoal of triacetyl glycerine production for a long time filled up by f, this adsorbent or other sorbing material is undesirable for the follow-up refining effect of product, the blank of shortage system research, has the meaning of extremely important reality.
The specific embodiment
Below in conjunction with the specific embodiment, the present invention is further described.
embodiment 1
Biological binary compound adsorbent in triacetyl glycerine process for refining, adopts beta-schardinger dextrin-, water and graininess cocoanut active charcoal as raw material, is prepared according to following steps:
Take respectively cyclodextrin 4 kg according to the ratio of cyclodextrin: water=0.04:1, water 100 kg; Water is put into the container that band stirs, add thermal agitation, in the time that temperature reaches and remain on 45 ℃, cyclodextrin is divided and add for four times in proportion, add 1kg at every turn, continue to keep temperature, control mixing speed 60r/min, treat that cyclodextrin all adds, be fully uniformly mixed, and mix; By the cyclodextrin solution heating preparing, temperature remains on 70 ℃, makes cyclodextrin hydrate; According to cyclodextrin hydrate: active carbon=1:0.05, take respectively granular cocoanut active charcoal 5 kg and cyclodextrin hydrate 100kg, and granular cocoanut active charcoal is added in cyclodextrin hydrate, after stirring, be heated to 90 ℃, stir and keep 60 minutes; Stop afterwards heating and stir, mixture is taken out, being placed in baking oven, being heated to 110 ℃ of oven dry, controlling moisture 1%; Mixture after drying is taken out, in hothouse, be cooled to normal temperature, pulverize, sieve, control granularity and obtain biological binary compound adsorbent at 300 orders.
By common acticarbon and this adsorbent respectively equivalent be applied in triacetyl glycerine process for refining, triacetyl glycerine product after treatment is detected, main organic substance residues is contrasted, concrete data see the following form:
Residual organic matter contrast in triacetyl glycerine
Can find out, adopt the biological binary compound adsorbent of the present embodiment to carry out refinement treatment to triacetyl glycerine, can remove or reduce organic impurities residual in product, guarantee triacetyl glycerine product index higher than in YC144-2008 standard about the requirement of organic impurities limit value.
embodiment 2
Biological binary compound adsorbent in triacetyl glycerine process for refining, adopts a-cyclodextrin, water and spherical active fruit shell carbon as raw material, is prepared according to following steps:
Take respectively cyclodextrin 12 kg according to the ratio of cyclodextrin: water=0.12:1, water 100 kg; Water is put into the container that band stirs, add thermal agitation, in the time that temperature reaches and remain on 50 ℃, cyclodextrin is divided and add for four times in proportion, add 3kg at every turn, continue to keep temperature, control mixing speed 60r/min, treat that cyclodextrin all adds, be fully uniformly mixed, and mix; By the cyclodextrin solution heating preparing, temperature remains on 70 ℃, makes cyclodextrin hydrate; According to cyclodextrin hydrate: active carbon=1:0.06, take respectively spherical active fruit shell carbon 7 kg and cyclodextrin hydrate 117kg, and spherical active fruit shell carbon is added in cyclodextrin hydrate, after stirring, be heated to 90 ℃, stir and keep 60 minutes; Stop afterwards heating and stir, mixture is taken out, being placed in baking oven, being heated to 110 ℃ of oven dry, controlling moisture to 1.5%; Mixture after drying is taken out, in hothouse, be cooled to normal temperature, pulverize, sieve, control granularity and obtain biological binary compound adsorbent at 300 orders.
By common acticarbon and this adsorbent respectively equivalent be applied in triacetyl glycerine process for refining, triacetyl glycerine product after treatment is detected, main organic substance residues is contrasted, concrete data see the following form:
Residual organic matter contrast in triacetyl glycerine
Can find out, adopt the biological binary compound adsorbent of the present embodiment to carry out refinement treatment to triacetyl glycerine, can remove or reduce organic impurities residual in product, guarantee triacetyl glycerine product index higher than in YC144-2008 standard about the requirement of organic impurities limit value.
embodiment 3
Biological binary compound adsorbent in triacetyl glycerine process for refining, adopts gamma-cyclodextrin, water and cylindrical cocoanut active charcoal as raw material, is prepared according to following steps:
Take respectively cyclodextrin 28 kg according to the ratio of cyclodextrin: water=0.28:1, water 100 kg; Water is put into the container that band stirs, add thermal agitation, in the time that temperature reaches and remain on 45 ℃, cyclodextrin is divided and add for four times in proportion, add 7kg at every turn, continue to keep temperature, control mixing speed 60r/min, treat that cyclodextrin all adds, be fully uniformly mixed, and mix; By the cyclodextrin solution heating preparing, temperature remains on 70 ℃, makes cyclodextrin hydrate; According to cyclodextrin hydrate: active carbon=1:0.07, take respectively cylindrical cocoanut active charcoal 7 kg and cyclodextrin hydrate 100kg, and cylindrical cocoanut active charcoal is added in cyclodextrin hydrate, after stirring, be heated to 90 ℃, stir and keep 60 minutes; Stop afterwards heating and stir, mixture is taken out, being placed in baking oven, being heated to 110 ℃ of oven dry, controlling moisture to 1.5%; Mixture after drying is taken out, in hothouse, be cooled to normal temperature, pulverize, sieve, control granularity and obtain biological binary compound adsorbent at 200 orders.
By common acticarbon and this adsorbent respectively equivalent be applied in triacetyl glycerine process for refining, triacetyl glycerine product after treatment is detected, main organic substance residues is contrasted, concrete data see the following form:
Residual organic matter contrast in triacetyl glycerine
Can find out, adopt the biological binary compound adsorbent of the present embodiment to carry out refinement treatment to triacetyl glycerine, can remove or reduce organic impurities residual in product, guarantee triacetyl glycerine product index higher than in YC144-2008 standard about the requirement of organic impurities limit value.
embodiment 4
Biological binary compound adsorbent in triacetyl glycerine process for refining, adopts r-cyclodextrin, water and graininess cocoanut active charcoal as raw material, is prepared according to following steps:
Take respectively cyclodextrin 58 kg according to the ratio of cyclodextrin: water=0.58:1, water 100 kg; Water is put into the container that band stirs, add thermal agitation, in the time that temperature reaches and remain on 45 ℃, cyclodextrin is divided and add for four times in proportion, add 14.5kg at every turn, continue to keep temperature, control mixing speed 60r/min, treat that cyclodextrin all adds, be fully uniformly mixed, and mix; By the cyclodextrin solution heating preparing, temperature remains on 70 ℃, makes cyclodextrin hydrate; According to cyclodextrin hydrate: active carbon=1:0.10, take graininess cocoanut active charcoal 7 kg and cyclodextrin hydrate 70kg, and graininess cocoanut active charcoal is added in cyclodextrin hydrate, after stirring, be heated to 90 ℃, stir and keep 60 minutes; Stop afterwards heating and stir, mixture is taken out, being placed in baking oven, being heated to 110 ℃ of oven dry, controlling moisture is 1.8%; Mixture after drying is taken out, in hothouse, be cooled to normal temperature, pulverize, sieve, control granularity and obtain biological binary compound adsorbent at 200 orders.
By common acticarbon and this adsorbent respectively equivalent be applied in triacetyl glycerine process for refining, triacetyl glycerine product after treatment is detected, main organic substance residues is contrasted, concrete data see the following form:
Residual organic matter contrast in triacetyl glycerine
Can find out, adopt the biological binary compound adsorbent of the present embodiment to carry out refinement treatment to triacetyl glycerine, can remove or reduce organic impurities residual in product, guarantee triacetyl glycerine product index higher than in YC144-2008 standard about the requirement of organic impurities limit value.
Claims (4)
1. the preparation method of biological binary compound adsorbent in triacetyl glycerine process for refining, is characterized in that, adopts cyclodextrin, water and active carbon as raw material, is prepared according to following steps:
Calculate with weight ratio, take cyclodextrin and water according to the ratio of cyclodextrin: water=0.04～0.60:1;
Water is put into the container that band stirs, add thermal agitation, in the time that temperature reaches and keep 45-50 ℃, divide four equivalent to add cyclodextrin, keep temperature, control mixing speed 60r/min, treat that cyclodextrin all adds, and is fully uniformly mixed;
By the cyclodextrin solution heating preparing, temperature remains on 70-80 ℃, keeps 10min to make cyclodextrin hydrate;
Calculate with weight ratio, according to active carbon: cyclodextrin hydrate=0.05～0.1:1, take and active carbon is added in cyclodextrin hydrate, after stirring, be heated to 90 ℃, stir and keep 60 minutes;
Stop heating and stir, mixture is taken out, being placed in baking oven, being heated to 110 ℃ of oven dry, controlling moisture lower than 2%;
Mixture after drying is taken out, in hothouse, be cooled to normal temperature, pulverize, sieve, control granularity and obtain biological binary compound adsorbent at 200-300 order.
2. preparation method, is characterized in that, described active carbon form is any one of granular activated carbon, cylindrical active carbon, spherical activated charcoal.
3. preparation method, is characterized in that, described active carbon kind is any one of cocoanut active charcoal, active fruit shell carbon.
4. preparation method, is characterized in that, described cyclodextrin is any one of a-cyclodextrin, beta-schardinger dextrin-and gamma-cyclodextrin.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108339519A (en) * | 2018-03-06 | 2018-07-31 | 高姌 | Modified activated carbon absorbent and its preparation process for Adsorption hardly degraded organic substance |
| CN110732310A (en) * | 2019-11-08 | 2020-01-31 | 安徽潜隆机电科技有限公司 | gas mask environment-friendly chromium-free carbon and preparation method thereof |
| CN111926594A (en) * | 2020-08-21 | 2020-11-13 | 绍兴柯桥新都印染有限公司 | Rayon dyeing process |
| CN113209940A (en) * | 2021-06-18 | 2021-08-06 | 江苏乾汇和环保再生有限公司 | Porous activated carbon composite material and preparation method thereof |
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| CN101613275A (en) * | 2009-03-11 | 2009-12-30 | 云南玉溪环腾科工贸有限公司 | Atomizing raw materials is produced the method for glycerine triacetate |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613275A (en) * | 2009-03-11 | 2009-12-30 | 云南玉溪环腾科工贸有限公司 | Atomizing raw materials is produced the method for glycerine triacetate |
Non-Patent Citations (2)
| Title |
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| JAE H. KWON, ET AL.: "Surface modified activated carbon with -cyclodextrin - Part I. Synthesis and characterization", 《JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A: TOXIC/HAZARDOUS SUBSTANCES AND ENVIRONMENTAL ENGINEERING》 * |
| JAE H. KWON, ET AL.: "Surface modified activated carbon with -cyclodextrin - Part I. Synthesis and characterization", 《JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A: TOXIC/HAZARDOUS SUBSTANCES AND ENVIRONMENTAL ENGINEERING》, vol. 45, no. 13, 1 October 2010 (2010-10-01), pages 1775 - 1792 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108339519A (en) * | 2018-03-06 | 2018-07-31 | 高姌 | Modified activated carbon absorbent and its preparation process for Adsorption hardly degraded organic substance |
| CN110732310A (en) * | 2019-11-08 | 2020-01-31 | 安徽潜隆机电科技有限公司 | gas mask environment-friendly chromium-free carbon and preparation method thereof |
| CN111926594A (en) * | 2020-08-21 | 2020-11-13 | 绍兴柯桥新都印染有限公司 | Rayon dyeing process |
| CN113209940A (en) * | 2021-06-18 | 2021-08-06 | 江苏乾汇和环保再生有限公司 | Porous activated carbon composite material and preparation method thereof |
| CN113209940B (en) * | 2021-06-18 | 2022-07-29 | 江苏乾汇和环保再生有限公司 | Porous activated carbon composite material and preparation method thereof |
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