CN103276024B - Technology for producing trioctyl citrate by using cassava - Google Patents
Technology for producing trioctyl citrate by using cassava Download PDFInfo
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- CN103276024B CN103276024B CN201310186129.1A CN201310186129A CN103276024B CN 103276024 B CN103276024 B CN 103276024B CN 201310186129 A CN201310186129 A CN 201310186129A CN 103276024 B CN103276024 B CN 103276024B
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Abstract
The invention provides a technology for producing trioctyl citrate by using cassava. The technology is characterized by comprising the following steps of: fermenting cassava so as to prepare a mixture containing citric acid and cassava residues; carrying out filter pressing and separating on the mixture; adding calcium carbonate for reacting to obtain calcium citrate salt; adding sulfuric acid, filtering and separating to obtain a citric acid solution; removing metal cation impurities from the citric acid solution to obtain citric acid clear liquid; and adding octanol to the citric acid clear liquid, and esterifying to obtain the finished product trioctyl citrate. According to the technology for producing the trioctyl citrate, the citric acid clear liquid produced by using the cassava is used for producing citrate esters, the concentration of the produced citric acid finished product is reduced, the steam consumption and the power consumption are reduced, a number of working procedures for manufacturing the finished product citric acid are reduced, and lots of manpower resources are saved. The yield of the citric acid is reduced due to mother liquid circulation in the conventional finished product citric acid production process. According to the production technology, the yield of the citric acid can be increased, and the production cost of the trioctyl citrate is reduced.
Description
Technical field
The present invention relates to a kind of production technique of trioctyl lemon acid.
Background technology
Trioctyl lemon acid is a kind of citric acid ester plasticizer, non-toxic and safe, it is one of first-selected environment-friendly type softening agent of domestic and international plastic industry, there is the features such as consistency is good, speedup high efficiency, nontoxic, volatility is little, and the plastics low temperature flexing performance after its plasticising is good, when molten material to thermally-stabilised, nondiscoloration, its winter hardiness, photostabilization, water tolerance, mould resistance are good, but because price is relatively high, are mainly used at present the field that non-toxic and safe is high.The production technique of existing trioctyl lemon acid is Fig. 1, is mostly minute two steps, first with starting material such as corns, produces finished lemon/lime acid, and then with finished lemon/lime acid, as raw material, adds alcohol and form by esterification.Adopt aforesaid method production citrate main drawback to be: technique circuit is long, and citric acid yield is low, and production cost is high.
Summary of the invention
The object of the present invention is to provide the technique of producing trioctyl lemon acid with cassava that a kind of technique is simple, production cost is low.
The technical solution used in the present invention is: a kind of technique of producing trioctyl lemon acid with cassava, is characterized in that: comprise following process:
(1) by dry, not mouldy Cassava crushing, add water and be deployed into after pasty state, fermentation makes the mixture containing citric acid and manioc waste;
(2) mixture is heated to, after 70-80 ℃, through press filtration separation, obtain fermentation filtrate;
(3) at neutralization tank, fermentation filtrate is warming up to after 80 ℃, under normal pressure, adds calcium carbonate reaction, it is 5.5 that terminal pH value is controlled, then with the filtration of adhesive tape type filter, and with the hot wash calcium citrate salts of 80-90 ℃;
(4) calcium citrate salts is mixed with to 80% solution, inject the liquid level of reaction cylinder to 50%, start and stir and be heated to 60 ℃, slowly add sulfuric acid, when pH value stops adding sulfuric acid in 3 left and right, after being heated to 85 ℃, with sulfuric acid or calcium citrate salts, adjust PH to 3, and keep after 30min, then add gac; After above-mentioned reaction completes, with adhesive tape type filter, isolate calcium sulfate, filtrate is citric acid solution;
(5) citric acid solution is pumped into from handing over post to remove metallic cation foreign material and obtains citric acid clear liquid with acid proof pump;
(6) citric acid clear liquid is proceeded in esterifying kettle, and add octanol in the ratio of citric acid and octanol mol ratio 1:3.5, drop into sulfuric acid simultaneously, utilize the boiling point of octanol higher than the principle of the boiling point of water, heat up and isolate moisture, when still temperature is 110 ℃, add light calcium powder, and drop into catalyzer, the alcohol that continues to heat up and to reflux, to citric acid total overall reaction generation ester in still, acidity completes in 0.2% esterification when following after testing; Then the aqueous sodium carbonate that is cooled to 80 ℃ of inputs 10% neutralizes, to remove residual acidic substance and catalyzer, alkali lye layer is removed in layering, then 80 ℃ of washing layerings, removes moisture content with pure water, add gac and be warming up to more than 165 ℃, removing residual excessive octanol;
(7) after material in reaction cylinder being filtered by fine filting machine, get final product to obtain finished lemon/lime acid three monooctyl esters.
The present invention produces trioctyl lemon acid and produces citrate with the citric acid clear liquid that cassava produces, and has reduced concentrated steam consumption quantity and the power consumption of having reduced of making citric acid finished product; Reduce many operations of making finished lemon/lime acid, saved a large amount of manpower; And the citric acid that originally manufactured a finished product has Recycling Mother Solution, can reduce the yield of citric acid, uses explained hereafter of the present invention, can improve the yield of citric acid, reduce the production cost of trioctyl lemon acid.
Accompanying drawing explanation
Fig. 1 is existing production lemon acid three monooctyl ester process flow sheets;
Fig. 2 is process flow sheet of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, it should be understood that these embodiment, only for the object of illustration, never limit the scope of the invention.
The embodiment of the present invention adopts as the technical process of Fig. 2, is specially:
1, by dry, not mouldy Cassava crushing to 60-80 order, with cassava per ton, adding 5 tons, water is deployed into after pasty state, according to cassava per ton, add liquid amylase 2 0ml and ammonium sulfate 0.6KG again, and be warming up to after 85 ℃, insulation 30min, then be warming up to 105 ℃ and be incubated 15min, sterilization and disinfection, after be cooled to 38 ℃ of left and right, add citric acid fermentation bacterial classification aspergillus niger, the about 55-60 hour that ferments makes containing the citric acid of 10%-15% and manioc waste mixture;
2, mixture is heated to, after 70-80 ℃, after manioc waste is isolated in press filtration, obtain the fermentation filtrate that contains citric acid;
3, the fermentation filtrate that contains citric acid is warming up to after neutralization tank to 80 ℃ of left and right, add under calcium carbonate normal pressure and react after 20-30min, control terminal pH value 5.5 left and right, with adhesive tape type filter, filter, and with the hot wash calcium citrate salts of 80-90 ℃, and with 0.1% potassium permanganate solution check, take redness in 5min and do not disappear as qualified;
4, citrate of lime is mixed with to 80% solution, inject the liquid level of reaction cylinder to 50%, start and stir and be heated to 60 ℃ of left and right, slowly add sulfuric acid, when pH value stops adding sulfuric acid in 3 left and right, more than being heated to 85 ℃, with sulfuric acid or calcium citrate salts, adjust PH to 3, and keep adding gac after 30min; After above-mentioned reaction completes, with adhesive tape type filter, isolate calcium sulfate, filtrate is citric acid solution;
5, citric acid solution is pumped into from handing over post to remove metallic cation foreign material and obtains citric acid clear liquid with acid proof pump;
6, citric acid clear liquid is proceeded in esterifying kettle, and add octanol in the ratio of citric acid and octanol mol ratio 1:3.5, drop into sulfuric acid simultaneously, utilize the boiling point (184 ℃) of octanol higher than the principle of the boiling point of water, the separated moisture content that heats up, when still temperature adds light calcium powder by the sulfuric acid amount dropping into during higher than 110 ℃, and drop into catalyzer, the octanol that continues to heat up and to reflux, to citric acid total overall reaction generation ester in still, acidity completes in 0.2% esterification when following after testing.The aqueous sodium carbonate that is cooled to about 80 ℃ inputs 10% neutralizes, to remove residual acidic substance.Alkali lye layer is removed in layering, then with pure water about 80 ℃ washings, moisture content is removed in layering, adds a small amount of gac and is warming up to more than 165 ℃, removes residual excessive octanol.Ester product reach qualified flash-point and obtain trioctyl lemon acid after testing;
7, get final product after material in reactor is filtered by fine filting machine and to obtain finished lemon/lime acid three monooctyl esters.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention; the technician of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications; these changes and improvements all fall in the claimed scope of the invention, and the claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (1)
1. with cassava, produce a technique for trioctyl lemon acid, it is characterized in that: comprise following process:
(1) by dry, not mouldy Cassava crushing, add water and be deployed into after pasty state, fermentation makes the mixture containing citric acid and manioc waste;
(2) mixture is heated to, after 70-80 ℃, through press filtration separation, obtain fermentation filtrate;
(3) at neutralization tank, fermentation filtrate is warming up to after 80 ℃, under normal pressure, adds calcium carbonate reaction, it is 5.5 that endpoint pH is controlled, then with the filtration of adhesive tape type filter, and with the hot wash calcium citrate salts of 80-90 ℃;
(4) calcium citrate salts is mixed with to 80% solution, inject the liquid level of reaction cylinder to 50%, start and stir and be heated to 60 ℃, slowly add sulfuric acid, when pH value stops adding sulfuric acid in 3 left and right, after being heated to 85 ℃, with sulfuric acid or calcium citrate salts, adjust pH to 3, and keep after 30min, then add gac; After above-mentioned reaction completes, with adhesive tape type filter, isolate calcium sulfate, filtrate is citric acid solution;
(5) citric acid solution is pumped into from handing over post to remove metallic cation foreign material and obtains citric acid clear liquid with acid proof pump;
(6) citric acid clear liquid is proceeded in esterifying kettle, and add octanol in the ratio of citric acid and octanol mol ratio 1:3.5, drop into sulfuric acid simultaneously, utilize the boiling point of octanol higher than the principle of the boiling point of water, heat up and isolate moisture, when still temperature is 110 ℃, add light calcium powder, and drop into catalyzer, the alcohol that continues to heat up and to reflux, to citric acid total overall reaction generation ester in still, acidity completes in 0.2% esterification when following after testing; Then the aqueous sodium carbonate that is cooled to 80 ℃ of inputs 10% neutralizes, to remove residual acidic substance and catalyzer, alkali lye layer is removed in layering, then 80 ℃ of washing layerings, removes moisture content with pure water, add gac and be warming up to more than 165 ℃, removing residual excessive octanol;
(7) after material in reaction cylinder being filtered by fine filting machine, get final product to obtain finished lemon/lime acid three monooctyl esters.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275975A (en) * | 1997-05-12 | 2000-12-06 | 莱利工业公司 | Processes for producing citrate esters |
| BR9904679A (en) * | 1999-10-29 | 2001-08-21 | Doutor Carlos Ricardo Soccol | Process of production of citric acid by fermentation in solid state using the fungus aspergillus niger |
| CN101693907A (en) * | 2009-11-06 | 2010-04-14 | 湖南洞庭柠檬酸化学有限公司 | Method for using dried potato flour to prepare potassium citrate |
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2013
- 2013-05-20 CN CN201310186129.1A patent/CN103276024B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275975A (en) * | 1997-05-12 | 2000-12-06 | 莱利工业公司 | Processes for producing citrate esters |
| BR9904679A (en) * | 1999-10-29 | 2001-08-21 | Doutor Carlos Ricardo Soccol | Process of production of citric acid by fermentation in solid state using the fungus aspergillus niger |
| CN101693907A (en) * | 2009-11-06 | 2010-04-14 | 湖南洞庭柠檬酸化学有限公司 | Method for using dried potato flour to prepare potassium citrate |
Non-Patent Citations (2)
| Title |
|---|
| 吴军 等.柠檬酸三辛酯的合成.《应用化工》.2004,第33卷(第1期), * |
| 柠檬酸三辛酯的合成;吴军 等;《应用化工》;20040229;第33卷(第1期);第58-60页，摘要、1.2实验方法部分 * |
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