CN102703557B - Preparation method for phytosterol acetate formed by catalytic synthesis through enzymic method - Google Patents
Preparation method for phytosterol acetate formed by catalytic synthesis through enzymic method Download PDFInfo
- Publication number
- CN102703557B CN102703557B CN 201210196274 CN201210196274A CN102703557B CN 102703557 B CN102703557 B CN 102703557B CN 201210196274 CN201210196274 CN 201210196274 CN 201210196274 A CN201210196274 A CN 201210196274A CN 102703557 B CN102703557 B CN 102703557B
- Authority
- CN
- China
- Prior art keywords
- preparation
- pyruvic acid
- plant sterol
- phytosterol
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title abstract description 7
- 238000007036 catalytic synthesis reaction Methods 0.000 title abstract 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229940107700 pyruvic acid Drugs 0.000 claims abstract description 22
- 239000004367 Lipase Substances 0.000 claims abstract description 13
- 102000004882 Lipase Human genes 0.000 claims abstract description 13
- 108090001060 Lipase Proteins 0.000 claims abstract description 13
- 235000019421 lipase Nutrition 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 235000002378 plant sterols Nutrition 0.000 claims description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002808 molecular sieve Substances 0.000 claims description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 12
- 102000004190 Enzymes Human genes 0.000 claims description 10
- 108090000790 Enzymes Proteins 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 235000019439 ethyl acetate Nutrition 0.000 claims description 5
- 230000003534 oscillatory effect Effects 0.000 claims description 2
- 230000032050 esterification Effects 0.000 abstract description 11
- 238000005886 esterification reaction Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012024 dehydrating agents Substances 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 description 17
- 229930182558 Sterol Natural products 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012207 quantitative assay Methods 0.000 description 4
- 235000003702 sterols Nutrition 0.000 description 4
- 150000003432 sterols Chemical class 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- -1 unsaturated fatty acid ester Chemical class 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229960004488 linolenic acid Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 229940075999 phytosterol ester Drugs 0.000 description 1
- 229940068065 phytosterols Drugs 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention relates to a preparation method for phytosterol acetate formed by catalytic synthesis through an enzymic method. The preparation method comprises the following steps: dissolving pyruvic acid and phytosterin as reaction substrates into dehydrated organic solvent; adding immobilized lipase and a dehydrating agent; and carrying out an oscillating reaction in a water bath of 40-60DEG C for 16-20 hours to obtain the phytosterol acetate, wherein the esterification rate is high as high as 93.01 percent. According to the preparation method disclosed by the invention, the phytosterol acetate is prepared from the pyruvic acid and the phytosterin as raw materials. The preparation method has the advantages of requirement on simple equipment, environment friendliness, safety and higher esterification rate.
Description
Technical field
The present invention relates to the preparing technical field of plant sterol ester, be specifically related to kind of the preparation method of enzyme law catalysis synthesizing phytosterol acetic ester.
Background technology
Plant sterol (phytosterols) has different physiological roles as a class natural active matter, be confirmed to be have reducing cholesterol, prevent prostatosis, anticancer, anti-inflammatory and regulate physiology hormonal readiness functional substance.Yet the low water solubility of plant sterol and oil soluble have limited it and directly have been developed to the possibility of heath food base-material, and synthetic plant sterol ester (PE) has not only improved its oil soluble, and keep its original biological activity.
Application number is that 200810059243.7 Chinese patent application disclose under comparatively high temps that to adopt calcium oxide and magnesium oxide be the catalyst reaction synthesizing phytosterol ester, high temperature has increased equipment requirements and dangerous coefficient, and reaction to remove catalyzer after finishing be a great problem; At article " preparation of plant sterol ester, biological activity and applied research " (doctorate paper, Wuhan: Hua Zhong Agriculture University, 2005) solubleness of report plant sterol polyunsaturated fatty acid ester in soybean salad oil is almost suitable with the solubleness of the plant sterol that dissociates in.
Chemical method synthesizing phytosterol unsaturated fatty acid ester has again the hidden danger that produces trans fatty acid, therefore, mainly adopts at present enzyme process synthesizing phytosterol unsaturated fatty acid ester both at home and abroad.In article " technical study of lipase-catalyzed synthesis alpha-linolenic acid plant sterol ester " (foodstuffs industry science and technology, 19 phases of the 29th volume, 2008) in be reported under the condition that lipase exists, alpha-linolenic acid and plant sterol are 55 ℃ in temperature of reaction, reaction 24h, esterification yield reaches 40.65%, and the reaction times is long and esterification yield is not high.
In recent years, appearance is about the report of synthesizing phytosterol and small molecules acid esters, article " chemosynthesis of plant sterol and Study of Antioxidation thereof " (master thesis, Wuxi: Southern Yangtze University, 2008) reports in that the solubleness of phytosterol acetate in fish oil is about 5 times of plant sterol.Domestic synthetic plant sterol small molecules acid esters is mainly phytosterol acetate at present, reported with chemical catalyst as reaction medium in the article " study on the synthesis of phytosterol acetate ", adopt plant sterol and diacetyl oxide to carry out the esterification building-up reactions and obtain phytosterol acetate, as everyone knows, there is larger potential safety hazard in diacetyl oxide, and chemical synthesis has also been suffered people's query at aspects such as security and environmental pollutions.
Summary of the invention
The object of the invention is to the series of problems that occurs in the practical application of plant sterol ester suitability for industrialized production, a kind of preparation method of enzyme law catalysis synthesizing phytosterol acetic ester is provided, take pyruvic acid and plant sterol ester as raw material, take lipase as catalyzer, heated and stirred prepares phytosterol acetate: the method requirement equipment is simple to operation, mild condition easily realizes, the materials safety that adopts, pollution-free, and esterification yield is high, and separation and purification obtains sterling easily.
The object of the invention is achieved through the following technical solutions.
A kind of preparation method of enzyme law catalysis synthesizing phytosterol acetic ester, the method is dissolved in the organic solvent that anhydrates take pyruvic acid and plant sterol as reaction substrate, adds immobilized lipase and dewatering agent, oscillatory reaction is 16 ~ 20 hours under 40 ~ 60 ℃ of water-baths, obtains phytosterol acetate.
Preferably, described pyruvic acid substitutes with the organic acid that contains the mineral acid of pyruvic acid or contain pyruvic acid.
Preferably, the mol ratio of described plant sterol and pyruvic acid is 1:2 ~ 1:6.
Preferably, the described organic solvent that anhydrates is the normal hexane that processed is crossed.
Preferably, described dissolving be with reaction substrate with put into water-bath constant temperature oscillator after the organic solvent that anhydrates mixes, mix 40 ~ 60 ℃ of vibrations.
Preferably, the add-on of described lipase is 5%～6% of pyruvic acid quality, more preferably 5% of the quality of pyruvic acid.
Preferably, described dewatering agent is molecular sieve, and add-on is the 40mg/mL reaction solvent.
Compared with prior art, technical superiority of the present invention is:
1) production unit is simple, and working condition easily reaches, and the technological process of production is short, is convenient to suitability for industrialized production;
2) adopt the reaction of pyruvic acid and plant sterol, higher esterification yield, safe is arranged, without side reaction, environmental protection, be convenient to product application in aspects such as food, medical and health;
3) not only conditional request is relatively gentle take immobilized lipase as catalyzer, and catalyzer very easily separates, and immobilized lipase can also reuse.
4) adopt molecular sieve as dewatering agent, avoid with organic solvent as the problems such as waste with aqua pollution on the environment and solvent;
5) relative plant sterol, about 5 times of its fat-soluble raising; Have than higher fat-soluble of plant sterol chain saturated fatty acids ester, and can not bring the harm such as trans fatty acid.
Embodiment
Below in conjunction with example implementation of the present invention is described further, but enforcement of the present invention and protection domain are not limited to this.
Embodiment 1
With being housed, plant sterol and the pyruvic acid that mol ratio is 1:5 add in the 150mL ground triangular flask, add the normal hexane that the 10mL processed is crossed, put into water-bath constant temperature oscillator, 55 ℃, fully vibration mixes 30min, and the question response thing dissolves fully, add 5%wt lipase (take the quality of pyruvic acid as benchmark) as catalyzer, 40mg/mL (addition of molecular sieve is 40mg in the unit volume reaction solvent) molecular sieve is as dewatering agent, and 55 ℃, reaction finished after 18 hours under the agitation condition.After the question response liquid cooling but, with the reaction solution suction filtration, isolate completely sterol of enzyme, molecular sieve and a small amount of unreacted, if filtrate still has a small amount of muddiness again to filter, at visible light 640nm place stronger absorption peak is arranged according to plant sterol ester, the amount of quantitative assay plant sterol ester, obtaining esterification yield is 93.01%.
Embodiment 2
With being housed, plant sterol and the pyruvic acid that mol ratio is 1:5 add in the 150mL ground triangular flask, add the normal hexane that the 10mL processed is crossed, put into water-bath constant temperature oscillator, 55 ℃, fully vibration mixes 30min, and the question response thing dissolves fully, add 6% lipase (take the amount of pyruvic acid as benchmark) as catalyzer, the 40mg/mL molecular sieve is as dewatering agent, and 55 ℃, reaction finished after 16 hours under the agitation condition.After the question response liquid cooling but, with the reaction solution suction filtration, isolate completely sterol of enzyme, molecular sieve and a small amount of unreacted, if filtrate still has a small amount of muddiness again to filter, at visible light 640nm place stronger absorption peak is arranged according to plant sterol ester, the amount of quantitative assay plant sterol ester, obtaining esterification yield is 91.25%.
Embodiment 3
With being housed, plant sterol and the pyruvic acid that mol ratio is 1:4 add in the 150mL ground triangular flask, add the normal hexane that the 10mL processed is crossed, put into water-bath constant temperature oscillator, 55 ℃, fully vibration mixes 30min, and the question response thing dissolves fully, add 5% lipase (take the amount of pyruvic acid as benchmark) as catalyzer, the 40mg/mL molecular sieve is as dewatering agent, and 55 ℃, reaction finished after 20 hours under the agitation condition.After the question response liquid cooling but, with the reaction solution suction filtration, isolate completely sterol of enzyme, molecular sieve and a small amount of unreacted, if filtrate still has a small amount of muddiness again to filter, at visible light 640nm place stronger absorption peak is arranged according to plant sterol ester, the amount of quantitative assay plant sterol ester, obtaining esterification yield is 87.90%.
Embodiment 4
With being housed, plant sterol and the pyruvic acid that mol ratio is 1:5 add in the 150mL ground triangular flask, add the normal hexane that the 10mL processed is crossed, put into water-bath constant temperature oscillator, 50 ℃, fully vibration mixes 30min, and the question response thing dissolves fully, add 5% lipase (take the amount of pyruvic acid as benchmark) as catalyzer, the 40mg/mL molecular sieve is as dewatering agent, and 50 ℃, reaction finished after 18 hours under the agitation condition.After the question response liquid cooling but, with the reaction solution suction filtration, isolate completely sterol of enzyme, molecular sieve and a small amount of unreacted, if filtrate still has a small amount of muddiness again to filter, at visible light 640nm place stronger absorption peak is arranged according to plant sterol ester, the amount of quantitative assay plant sterol ester, obtaining esterification yield is 86.72%.
Claims (2)
1. the preparation method of an enzyme law catalysis synthesizing phytosterol acetic ester, it is characterized in that, take pyruvic acid and plant sterol as reaction substrate, be dissolved in the organic solvent that anhydrates, add immobilized lipase and dewatering agent, oscillatory reaction is 16 ~ 20 hours under 40 ~ 60 ℃ of water-baths, obtains phytosterol acetate; The described organic solvent that anhydrates is the normal hexane that processed is crossed; Described dewatering agent is molecular sieve, and add-on is the 40mg/mL organic solvent; The mol ratio of described plant sterol and pyruvic acid is 1:2 ~ 1:6; The add-on of described lipase is 5%～6% of pyruvic acid quality.
2. preparation method according to claim 1 is characterized in that, described dissolving be with reaction substrate with put into water-bath constant temperature oscillator after the organic solvent that anhydrates mixes, mix 40 ~ 60 ℃ of vibrations.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210196274 CN102703557B (en) | 2012-06-14 | 2012-06-14 | Preparation method for phytosterol acetate formed by catalytic synthesis through enzymic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210196274 CN102703557B (en) | 2012-06-14 | 2012-06-14 | Preparation method for phytosterol acetate formed by catalytic synthesis through enzymic method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102703557A CN102703557A (en) | 2012-10-03 |
| CN102703557B true CN102703557B (en) | 2013-10-30 |
Family
ID=46896603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210196274 Expired - Fee Related CN102703557B (en) | 2012-06-14 | 2012-06-14 | Preparation method for phytosterol acetate formed by catalytic synthesis through enzymic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102703557B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111876406B (en) * | 2020-06-18 | 2022-05-03 | 南京师范大学 | Magnetic nanoparticle-lipase-metal organic framework composite catalytic material and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263769C (en) * | 2004-06-24 | 2006-07-12 | 浙江大学 | Method for separating and extracting cholesterol from lanolin |
| CN1318601C (en) * | 2005-03-24 | 2007-05-30 | 合肥工业大学 | New separation technology of vitamin E, sterol and sterol ester in vegetable oil deodorization distillate |
| CN102351935A (en) * | 2011-08-02 | 2012-02-15 | 安徽农业大学 | Method for preparing sterol monomer separated from mixed plant sterol |
-
2012
- 2012-06-14 CN CN 201210196274 patent/CN102703557B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102703557A (en) | 2012-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102660593B (en) | Method for preparing glyceride rich in algal oil n-3 polyunsaturated fatty acid through enzyme process | |
| CN105219813B (en) | A kind of method that enzyme process prepares bis- oleic acid -2- palmitic acid of 1,3-, three ester in subcritical system | |
| CN100491244C (en) | Method for preparing active carbon from stalk of wheat | |
| CN102757988A (en) | Preparation method of 1,3-dioleoyl-2-palmitoyl triglyceride | |
| CN101845473A (en) | Method for effectively synthesizing phytosterol ester | |
| CN1927710A (en) | Method of preparing activated carbon from corn straw | |
| CN111094312B (en) | Preparation method of sucrose ester | |
| CN105152980A (en) | Chiral preparation method for N-t-butyloxycarboryl-(4S)-(p-phenyl phenyl methyl)-4-amino-(2R)-methylbutyric acid | |
| CN101544677B (en) | Phytosterin fatty acid ester and preparation method thereof | |
| CN102268464A (en) | Method for producing diglyceride with rice bran oil of high acid value | |
| CN101475968B (en) | Method for synthesizing natural alpha-tocofecol tocopherol acid succinate by using lipase | |
| CN102703557B (en) | Preparation method for phytosterol acetate formed by catalytic synthesis through enzymic method | |
| CN107805647A (en) | A kind of method of backbone ester in enzymatic clarification | |
| CN102320953A (en) | Method for preparing natural alpha-linolenic acid from crude oil of idesia polycarpa var.vestita diels | |
| Das et al. | Biogenic palladium nanostructures for Suzuki-Miyaura and Sonogashira cross-coupling reaction under mild reaction conditions | |
| CN106591385B (en) | Method for preparing butyrin by enzyme method | |
| CN101457240B (en) | Method for preparing citronellyl by bioconversion in non-aqueous phase system | |
| CN108531538A (en) | A kind of method that enzyme process prepares phytosterin ester | |
| CN1137975C (en) | Process for preparing conjugated linoleic acid from dewatered castor oil | |
| JPS6388159A (en) | Production of docosahexaenoic acid ester | |
| CN102531892A (en) | Method for preparing diacylglycerol | |
| CN105195206B (en) | Alkali modification molecular sieve prepares the application of CLA catalysts as corn oil conjugation | |
| CN101279962A (en) | Method for preparing L-ascorbyl palmitate from biodiesel by-product | |
| CN101948882A (en) | Method for synthesizing L-ascorbic acid oleate by using nonaqueous phase enzyme | |
| CN105296554B (en) | Combined-enzyme method prepares the preparation method of pneumatically conveying |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131030 |