CN105483169A - Method for producing aliphatic acid through utilization of gutter cooking oil in enzymic method - Google Patents

Method for producing aliphatic acid through utilization of gutter cooking oil in enzymic method Download PDF

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Publication number
CN105483169A
CN105483169A CN201410465711.6A CN201410465711A CN105483169A CN 105483169 A CN105483169 A CN 105483169A CN 201410465711 A CN201410465711 A CN 201410465711A CN 105483169 A CN105483169 A CN 105483169A
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China
Prior art keywords
oil
hydrolysis
sewer oil
lipid acid
water
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CN201410465711.6A
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Chinese (zh)
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不公告发明人
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HUAINAN LANCAI ENVIRONMENTAL PROTECTION TECHNOLOGY CO LTD
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HUAINAN LANCAI ENVIRONMENTAL PROTECTION TECHNOLOGY CO LTD
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Priority to CN201410465711.6A priority Critical patent/CN105483169A/en
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Abstract

The invention discloses a method for producing aliphatic acid through utilization of gutter cooking oil in an enzymic method. The method comprises the following steps: (1) heating gutter cooking oil while stirring and contacting gutter cooking oil with carbon dioxide and water to generate acidified oil; (2) washing acidified oil with water to remove water and impurities and to obtain neutral acidified oil with relatively high purity; (3) mixing acidified oil and neutral lipase for a hydrolysis reaction to obtain a hydrolyzed mixed product; and (4) separating an upper oil substance from the hydrolyzed mixed product in a separation tank and washing the upper oil substance with water to obtain the mixed aliphatic acid. The method has advantages of low energy consumption, less equipment investment, simple process, simple operation, and low production cost. The method is adapted to production with different scales, and is beneficial for comprehensive and full utilization of resources. Environment pollution is reduced, and a working condition is improved.

Description

A kind of method utilizing sewer oil Production by Enzymes lipid acid
Technical field
The present invention relates to a kind of method of producing lipid acid, particularly relate to a kind of method utilizing sewer oil Production by Enzymes lipid acid.
Background technology
According to statistics, China has 2,600 ten thousand tons of sewer oils for 1 year, and it is social as the raw material harm of producing edible oil by lawless person that these sewer oils have.Heavy metal in sewer oil, toxin (as propenal) severe overweight, peroxide value is higher than 0.4%, and considerably beyond national standard 0.15%, long-term absorption can make cell function exhaustion, brings out various diseases, even carcinogenic.Be that main raw material extracts the technical process of lipid acid and do not have secondary pollution with sewer oil, in technical process, use enzyme as catalyzer, make changing waste into resources, minimizing, innoxious, reach the requirement of cleaner production and recycling economy.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of equipment is simple, energy-conserving and environment-protective, Production by Enzymes lipid acid that cost is low method.
Utilize a method for sewer oil Production by Enzymes lipid acid, comprise the steps:
(1) sewer oil (removal of impurities) is heated, stir and contact with water with carbonic acid gas, generate acidification oil;
(2) washed by acidification oil, removing moisture and impurity, obtain quinaldine acid carburetion;
(3) quinaldine acid carburetion is mixed with neutral lipase carry out hydrolysis reaction, obtain being hydrolyzed mix products;
(4) described hydrolysis mix products is isolated upper oil phase material in separating tank, obtain mixed fatty acid after washing, i.e. product.
The principal reaction of the method for the invention is: C 3h 5(OORn) 3→ C 3h 5(OH) 3+ RnCOOH
The method utilizing sewer oil Production by Enzymes lipid acid of the present invention, wherein, the described hydrolysis reaction in step (3) carries out at twice: mixed with lipase by acidification oil and carry out first time hydrolysis reaction, obtain the first hydrolysis mix products; Described first hydrolysis mix products enters separating tank, removing moisture and impurity, and upper oil phase and lipase carry out second time hydrolysis reaction, obtain the second hydrolysis mix products;
Described second hydrolysis mix products is isolated upper oil phase material in separating tank, obtains mixed fatty acid after washing, i.e. product.
The method utilizing sewer oil Production by Enzymes lipid acid of the present invention, wherein also comprises the steps: after step (4)
(5) lipid acid of different carbon chain is obtained after being refined as required by described mixed fatty acid.
The method utilizing sewer oil Production by Enzymes lipid acid of the present invention, wherein described in step (1), contact process is carried out in a heated condition, temperature is 70 ~ 85 DEG C, the pressure of described carbonic acid gas is 0.3 ~ 0.6MP, the time of contact is 5 ~ 12h, and the total amount of described sewer oil and the weight ratio of water are 2 ~ 10.When pressure carbon dioxide is lower than 0.1MP, the solvability of carbonic acid gas in water is poor, and the acidity of the aqueous solution obtained is more weak, effectively sewer oil can not be carried out acidifying, causes the yield of acidification oil on the low side; When pressure carbon dioxide is higher than 1MP, the quality of acidification oil does not significantly improve, and then requires higher to the voltage endurance capability of reaction vessel.
The method utilizing sewer oil Production by Enzymes lipid acid of the present invention, the pressure of wherein said carbonic acid gas is 0.3 ~ 0.6MP, and temperature of reaction is 70 ~ 85 DEG C, and the time of contact is 5 ~ 12h, and the total amount of sewer oil and the weight ratio of water are 2 ~ 10.
The method utilizing sewer oil Production by Enzymes lipid acid of the present invention, wherein lipase described in step (3) is neutral or acid, and described hydrolysis is carried out under normal temperature, normal pressure, pH value neutrallty condition.Described lipase is neutral lipase or acid lipase enzyme, and acid lipase enzyme can acidproof (PH3 ~ 5), neutral lipase (PH6 ~ 11), and needs to adjust pH value with alkaline lipase (PH8 ~ 11), raises the cost and effect is not remarkable.
The method utilizing sewer oil Production by Enzymes lipid acid of the present invention, wherein said hydrolysis temperature is 30 ~ 50 DEG C.
The method utilizing sewer oil Production by Enzymes lipid acid of the present invention, wherein said method also comprises sweet oil recovery.
The method difference from prior art of sewer oil Production by Enzymes lipid acid that utilizes of the present invention is to the invention discloses employing high concentration CO 2the aqueous solution substitutes dense sulfuric acid treatment sewer oil, isolate acidification oil, the high concentration CO 2 aqueous solution has stronger acidity, the acidifyings such as trench well cuts can be made and be separated, and the supercarbonate generated can as ionogen, soluble in water, destroy colloidal structure, neutral oil and lipid acid are assembled, thus comes with other separating substances; CO 2be gas, be easy to and solution separating after step-down, the acidification oil purity obtained is high, environmentally safe, and the waste water of discharge is not containing acid, simple to operate.The acidification oil that sulfuric acid process obtains is chocolate, and purity is low.Sewer oil reclaims and utilizes by the method for the invention, turns waste into wealth, greatly reduces cost while energy-conserving and environment-protective; Enzymatic hydrolysis sewer oil has the advantages such as power consumption is low, facility investment is few, flow process is simple, and easy and simple to handle, tooling cost is low, is suitable for different scales and produces, be conducive to comprehensive utilization and make full use of resource, reduces environmental pollution and improves working conditions; Be conducive to glycerine to reclaim, percent hydrolysis reaches more than 92% simultaneously; Sewer oil enzymatic hydrolysis is utilized to produce lipid acid, significant to development cleaner production, and have broad application prospects.
Embodiment
Embodiment 1
Utilize a method for sewer oil Production by Enzymes lipid acid, comprise the steps:
(1) sewer oil (removal of impurities) is heated, stir and contact with water with carbonic acid gas, generate acidification oil; Contact process is carried out in a heated condition, and temperature is 60 ~ 90 DEG C, and the pressure of described carbonic acid gas is 0.1 ~ 1MP, and the time of contact is 5 ~ 20h, and the total amount of described sewer oil and the weight ratio of water are 1 ~ 20;
(2) washed by acidification oil, removing moisture and impurity, obtain quinaldine acid carburetion;
(3) quinaldine acid carburetion is mixed with lipase carry out hydrolysis reaction, obtain being hydrolyzed mix products; Described lipase is neutral or acid, and described hydrolysis is carried out under normal temperature, normal pressure, pH value neutrallty condition; Described hydrolysis temperature is 30 ~ 50 DEG C;
(4) described hydrolysis mix products is isolated upper oil phase material in separating tank, obtain mixed fatty acid after washing, i.e. product.
Embodiment 2
Utilize a method for sewer oil Production by Enzymes lipid acid, the pressure of wherein said carbonic acid gas is 0.3 ~ 0.8MP, and the temperature of contact is 70 ~ 85 DEG C, and the time of contact is 5 ~ 10h, and the total amount of sewer oil and the weight ratio of water are 1 ~ 10; Described method also comprise after step (4) described mixed fatty acid is refining as required after obtain the lipid acid of different carbon chain, other are with embodiment 1.
Embodiment 3
Utilize a method for sewer oil Production by Enzymes lipid acid, described method also comprises and reclaiming glycerine, and other are with embodiment 2.
Embodiment 4
Utilize a method for sewer oil Production by Enzymes lipid acid, comprise the steps:
(1) by sewer oil (removal of impurities) heat, stir and carbonic acid gas contact with water, generation acidification oil; Described contact process is carried out in a heated condition, and temperature is 75 ~ 80 DEG C, and the pressure of described carbonic acid gas is 0.3 ~ 0.6MP, and the time of contact is 5 ~ 12h, and the total amount of described sewer oil and the weight ratio of water are 2 ~ 10;
(2) washed by acidification oil, removing moisture and impurity, obtain quinaldine acid carburetion; Abundant reacted mixture should divide three layers, is followed successively by oil phase, plant asphalt and aqueous phase from top to bottom, and separating tank removing plant asphalt and aqueous phase, separate the upper oil phase comprising acidification oil;
(3) acidification oil is mixed with lipase carry out first time hydrolysis reaction, obtain the first hydrolysis mix products; Described first hydrolysis mix products enters separating tank, removing moisture and impurity, and upper oil phase and lipase carry out second time hydrolysis reaction, obtain the second hydrolysis mix products;
(4) described second hydrolysis mix products is isolated upper oil phase material in separating tank, obtain mixed fatty acid after washing, i.e. product.
Wherein, described lipase is neutral or acid, and described hydrolysis is carried out under normal temperature, normal pressure, pH value neutrallty condition, also comprises sweet oil recovery in reaction process.
Embodiment 5
Utilize a method for sewer oil Production by Enzymes lipid acid, described method also comprise after step (4) described mixed fatty acid is refining as required after obtain the lipid acid of different carbon chain, other are with embodiment 4.
Embodiment 6
Utilize a method for sewer oil Production by Enzymes lipid acid, comprise the steps:
(1) sewer oil (removal of impurities) is heated, stir and contact with water with carbonic acid gas, generate acidification oil; Contact process is carried out in a heated condition, and temperature is 60 ~ 75 DEG C, and the pressure of described carbonic acid gas is 0.3 ~ 0.5MP, and the time of contact is 6 ~ 12h, and the total amount of described sewer oil and the weight ratio of water are 3 ~ 12;
(2) washed by acidification oil, removing moisture and impurity, obtain quinaldine acid carburetion;
(3) quinaldine acid carburetion is mixed with lipase carry out hydrolysis reaction, obtain being hydrolyzed mix products; Described lipase is neutral or acid, and described hydrolysis is carried out under normal temperature, normal pressure, pH value neutrallty condition; Described hydrolysis temperature is 40 DEG C;
(4) described hydrolysis mix products is isolated upper oil phase material in separating tank, after washing, obtain mixed fatty acid;
(5) obtain the lipid acid of different carbon chain after being refined as required by described mixed fatty acid, obtain product.
Wherein, sweet oil recovery is also comprised in described procedure.
Embodiment 7
Utilize a method for sewer oil Production by Enzymes lipid acid, comprise the steps:
(1) by sewer oil (removal of impurities) heat, stir and carbonic acid gas contact with water, generation acidification oil; Described contact process is carried out in a heated condition, and temperature is 65 ~ 80 DEG C, and the pressure of described carbonic acid gas is 0.5 ~ 1MP, and the time of contact is 5 ~ 9h, and the weight ratio of described sewer oil total amount and water is 5 ~ 15;
(2) washed by acidification oil, removing moisture and impurity, obtain quinaldine acid carburetion; Abundant reacted mixture should divide three layers, is followed successively by oil phase, plant asphalt and aqueous phase from top to bottom, and separating tank removing plant asphalt and aqueous phase, separate the upper oil phase comprising acidification oil;
(3) acidification oil is mixed with lipase carry out first time hydrolysis reaction, obtain the first hydrolysis mix products; Described first hydrolysis mix products enters separating tank, removing moisture and impurity, and upper oil phase and lipase carry out second time hydrolysis reaction, obtain the second hydrolysis mix products;
(4) described second hydrolysis mix products is isolated upper oil phase material in separating tank, obtain mixed fatty acid after washing, i.e. product.
Wherein, described lipase is neutral or acid, and described hydrolysis is carried out under normal temperature, normal pressure, pH value neutrallty condition, also comprises sweet oil recovery in reaction process.
Embodiment 8
Utilize a method for sewer oil Production by Enzymes lipid acid, comprise the steps:
(1) sewer oil (removal of impurities) is heated, stir and contact with water with carbonic acid gas, the pressure of carbonic acid gas is 0.5 ~ 0.9MP, and the temperature of contact is 60 ~ 85 DEG C, and the time of contact is 5 ~ 10h, the total amount of sewer oil and the weight ratio of water are 2 ~ 10, isolate acidification oil;
(2) in 2000ml tetra-mouthfuls of reactors, 100 grams of acidification oils are added, add appropriate phosphate buffer solution and neutral or acid lipase enzyme, at 40 DEG C, 100 revs/min of stirring reaction 36h, the acidification oil hydrolyzed solution obtained adopts acidity analysis method to measure, its acid value is 143mgKOH/g, and calculating percent hydrolysis according to aforesaid method is 85 ~ 90%.The hydrolyzed solution stratification obtained, separates the thick finger fat acid that aqueous phase can obtain containing a small amount of water.
(3) croude fatty acids containing a small amount of water is carried out underpressure distillation under vacuum tightness 90.6-93.3KPa, collect 200-240 DEG C of cut, described mixed fatty acid can be obtained.
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determines.

Claims (8)

1. utilize a method for sewer oil Production by Enzymes lipid acid, it is characterized in that, comprise the steps:
(1) sewer oil is heated, stir and contact with water with carbonic acid gas, generate acidification oil;
(2) abundant reacted mixture washing, removing moisture and impurity, obtain quinaldine acid carburetion;
(3) acidification oil is mixed with neutral lipase carry out hydrolysis reaction, obtain being hydrolyzed mix products;
(4) described hydrolysis mix products is isolated upper oil phase material in separating tank, obtain mixed fatty acid after washing, i.e. product.
2. the method utilizing sewer oil Production by Enzymes lipid acid according to claim 1, it is characterized in that: the described hydrolysis reaction in step (3) carries out at twice: acidification oil is mixed with neutral lipase and carries out first time hydrolysis reaction, obtain the first hydrolysis mix products; Described first hydrolysis mix products enters separating tank, and removing moisture and impurity, upper oil phase and lipase carry out second time hydrolysis reaction, obtain the second hydrolysis mix products.
3. the method utilizing sewer oil Production by Enzymes lipid acid according to claim 1 and 2, is characterized in that: also comprise the steps: after step (4)
(5) lipid acid of different carbon chain is obtained after being refined as required by described mixed fatty acid.
4. the method utilizing sewer oil Production by Enzymes lipid acid according to claim 3, it is characterized in that: described in step (1), process is carried out in a heated condition, temperature is 60 ~ 90 DEG C, the pressure of described carbonic acid gas is 0.1 ~ 1MP, the time of contact is 5 ~ 20h, and the total amount of described sewer oil (after removal of impurities) and the weight ratio of water are 1 ~ 20.
5. the method utilizing sewer oil Production by Enzymes lipid acid according to claim 4, it is characterized in that: the pressure of described carbonic acid gas is 0.3 ~ 0.6MP, temperature of reaction is 70 ~ 85 DEG C, and the time is 5 ~ 12h, and the total amount of sewer oil and the weight ratio of water are 2 ~ 10.
6. the method utilizing sewer oil Production by Enzymes lipid acid according to claim 4, is characterized in that: lipase described in step (3) is for neutral or acid, and described hydrolysis is carried out in neutral conditions in normal temperature, normal pressure, pH value.
7. the method utilizing sewer oil Production by Enzymes lipid acid according to claim 6, is characterized in that: described hydrolysis temperature is 30 ~ 50 DEG C.
8. the method utilizing sewer oil Production by Enzymes lipid acid according to claim 4 or 5 or 6 or 7, is characterized in that: described method also comprises sweet oil recovery.
CN201410465711.6A 2014-09-15 2014-09-15 Method for producing aliphatic acid through utilization of gutter cooking oil in enzymic method Pending CN105483169A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108277118A (en) * 2018-02-06 2018-07-13 宁波嘉和新材料科技有限公司 A kind of biomass-based surfactant and preparation method thereof containing trench oil extract
CN111303991A (en) * 2019-12-11 2020-06-19 江西省金泰茶脂开发有限公司 Preparation method of swill-cooked dirty oil fatty acid
CN113647385A (en) * 2021-08-23 2021-11-16 郯城众一科环化工有限公司 Preparation method of environment-friendly solvent
CN113699190A (en) * 2021-09-07 2021-11-26 龙口香驰粮油有限公司 Enzymolysis process of soapstock/oil foot

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108277118A (en) * 2018-02-06 2018-07-13 宁波嘉和新材料科技有限公司 A kind of biomass-based surfactant and preparation method thereof containing trench oil extract
CN111303991A (en) * 2019-12-11 2020-06-19 江西省金泰茶脂开发有限公司 Preparation method of swill-cooked dirty oil fatty acid
CN113647385A (en) * 2021-08-23 2021-11-16 郯城众一科环化工有限公司 Preparation method of environment-friendly solvent
CN113699190A (en) * 2021-09-07 2021-11-26 龙口香驰粮油有限公司 Enzymolysis process of soapstock/oil foot

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