CN106337069A - Fatty acid short chain ester two-step preparation technology - Google Patents
Fatty acid short chain ester two-step preparation technology Download PDFInfo
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Abstract
The invention provides a novel fatty acid short chain ester two-step preparation technology. The technology comprises completely hydrolyzing grease, separating C8-C24 fatty acid from a grease hydrolysate, preparing a fatty acid short chain ester through lipase catalytic fatty acid alcoholysis, after hydrolysis, returning the whole heavy phase to the hydrolysis system and carrying out repeated recycling. In an enzymatic alcoholysis reaction process, through control of short chain alcohol fed-batching and use of a mild on-line dehydration technology, by-product water-caused negative influence on lipase and a product yield is eliminated and complete conversion from fatty acid into fatty acid short chain ester is realized. The technology has the advantages of good grease raw material applicability, eco-friendly and clean processes and high product yield.
Description
Technical field
The invention belongs to biological chemical field, specifically, being related to two-step method, to prepare fatty acid short
The technique of chain ester.
Background technology
The high-valued conversion of oils and fatss has become the focus of domestic and international research.Wherein, oils and fatss are converted
Become long-chain fatty acid short-chain ester, can be used as the energy or biological lubricants.Produce fatty acid at present short
Chain ester mainly adopts chemical method, that is, use animal and plant fat and some low-carbon alcohols (methanol or ethanol)
Carry out ester exchange reaction under alkali or acidic catalyst effect, generate corresponding fatty acid methyl ester
Or ethyl ester.There is as follows inevitably shortcoming in chemical method preparation biodiesel: 1. to raw oil
The content of the free fatty in fat and water has strict demand；2. the saponified increasing that alkaline process easily generates
The big viscosity of reaction system and the detached difficulty of glycerol, acid system reaction temperature is higher, and equipment
Easily it is corroded；3. chemical method methanol usage substantially exceeds reaction mol ratio, the recovery of excessive methanol
Increase process energy consumption；4. produce the waste liquid containing spent acid or salkali waste in a large number in production process, environment is dirty
Dye is serious.There is reaction condition gently using biological enzyme synthetic fatty acid short-chain ester, run energy
Consumption is low, and non-pollutant discharge and have the advantages that the extensive glyceride stock suitability meets green
The developing direction of colour chemistry, thus it is increasingly subject to the attention of people.However, using Digestive Enzyme
When carrying out as catalyst, because the especially low-quality waste grease composition of oils and fatss is complicated, except
Outside containing glyceride, fatty acid, phospholipid, moisture, also contain a large amount of colloids and some other
Have a strong impact on the impurity component of enzymatic activity.The directly use of these low-quality glyceride stocks is to enzyme
Safety causes very big hidden danger.In addition, the utilization to enzyme reactor for the presence of these impurity substances
Isolating and purifying etc. of rate, the recovery of enzyme and subsequent product has negative effect, and this is in very great Cheng
Enzymatic conversion method oil and fat preparation fatty acid short-chain ester be also limit on degree to different glyceride stocks, especially
It is the suitability of low-quality glyceride stock.
Content of the invention
The purpose of the present invention is that to be inherently eliminated impurity in oils and fatss negative to enzyme catalysiss characteristic
Impact, provides two-step method to prepare the new technology of fatty acid short-chain ester, that is, pass through two step conversion process
Oils and fatss Efficient Conversion is fatty acid short-chain ester.
In order to realize the object of the invention, the two-step method of the present invention prepares the work of fatty acid short-chain ester
Skill, comprises the following steps:
Step one: oils and fatss are thoroughly hydrolyzed into fatty acid, and isolate from hydrolyzate
C8-c24 fatty acid.The c8-c24 fatty acid that hydrolysis obtains is made to separate from considerable impurity
Out.
Step 2: with lipase-catalyzed c8-c24 fatty acid, alcoholysis reaction occurs, the biological bavin of preparation
Oil.During enzymatic alcoholysis reaction, by controlling short-chain alcohol streams to add and carrying out online dehydration,
Eliminate the negative effect to Digestive Enzyme and efficiency of pcr product for the water byproduct, realize from fatty acid to fat
The conversion completely of sour short-chain ester.
Aforesaid technique, in step one, hydrolysis are directed to interval in one or more levels reactor
Or it is continuously added to oils and fatss and the water based on oil quality 50-1200% carries out the hydrolysis of oils and fatss, hydrolysis
Reaction, at 160-230 DEG C, is carried out under 1.5-3mpa.
Aforesaid technique, the heavy phase after hydrolysis finishes in step one can separate together, multiple reuse.
Aforesaid technique, step 2 is by c8-c24 fatty acid and to be based on unit oil quality
The Digestive Enzyme of 200-1000 enzyme-activity unit loads in one or more levels circulation flow reactor, by fat
There is esterification with short chain alcohol in fat enzyme catalysiss c8-c24 fatty acid, temperature of reactor controls
20-50 DEG C, c8-c24 fatty acid is 1:4-5 with the mol ratio of short chain alcohol, and described short chain alcohol is
Methanol, ethanol, propanol or butanol etc..
Aforesaid technique, during step 2 enzymatic alcoholysis reaction, carries out non-uniform flow and adds short chain alcohol
With gentle online dewatering process.
Wherein, described non-uniform flow add short chain alcohol refer to reaction 0 hour, 1 hour, 2 hours, 3
Hour and 3.5 hours, be separately added into the short chain alcohol of oils and fatss equimolar amountss.
Aforesaid technique, described online dehydration refers to using film, molecular sieve or short chain alcohol air stripping etc..
Wherein, described film is inoranic membrane, organic membrane or metal film；Described molecular sieve is
Molecular sieve；Described short chain alcohol air stripping is the tank by reactor side directly and equipped with anhydrous short chain alcohol
Even, the temperature of anhydrous short chain alcohol is 20-40 DEG C to body phase, and the opposite side of reactor is with vacuum pump even
Connect, then vacuum pump is connected with condenser, by vacuum control in reactor in 10-100mpa,
Condenser temperature is 5-15 DEG C.
Used in the present invention, Digestive Enzyme is included from yeast, mycete, antibacterial or other micro- life
The Digestive Enzyme of thing；Digestive Enzyme is the combination of single Digestive Enzyme or multiple Digestive Enzyme.For example, originate
In the Digestive Enzyme of aspergillus oryzae (aspergillus oryzae), from antarctic candida
The Digestive Enzyme of (candida antarctica), from rhizomucor miehei (rhizomucor
Miehei Digestive Enzyme) etc..
Used in the present invention glyceride stock be bio-oil, including Vegetable oil lipoprotein, animal oil,
The concise leftover bits and pieces of waste edible oil, acidification oil, oils and fatss and microbial grease etc..
Wherein, described Vegetable oil lipoprotein includes Oleum Ricini, Oleum Brassicae campestriss, soybean oil, Oleum Arachidis hypogaeae semen, jade
Miyou, Oleum Gossypii semen, Testa oryzae oil, curcas oil, shinyleaf yellowhorn oil, Jatropha curcas oil etc.；Described dynamic
Thing oils and fatss include fish oil, Adeps Sus domestica etc.；Described microbial grease includes yeast oils and fatss, microalgae oil
Fat etc..
The invention has the advantages that
The two-step method of the present invention prepares the technique of fatty acid short-chain ester, and oils and fatss are first entered by the first stage
Row hydrolysis, is then demultiplex out high-purity hydrolysis product fatty acid, it is outstanding that this can evade oils and fatss completely
It is the negative effect to subsequently lipase-catalyzed characteristic for the Various Complex composition in low-quality oils and fatss.
During the enzymatic fatty acid alcoholysis reaction of second stage prepares fatty acid short-chain ester, by control
Short-chain alcohol streams processed add and carry out gentle online dehydration technique so that fatty acid can convert completely
Product, and product is only the mixture of fatty acid short-chain ester and short chain alcohol, returns through simple distillation
Receive short chain alcohol, you can obtain high purity fatty acid short-chain ester product.This two-step process simultaneous interpretation
The technique that fatty acid short-chain ester is prepared in one step enzymatic oils and fatss conversion of system is compared, and significantly reduces oil
The impact to enzyme activity for the complicated ingredient in fat, additionally, in second step enzymatic oils and fatss alcoholysis reaction,
The material participating in reaction is high purity fatty acid, without neutral esters (triglyceride, diglyceride
And monoglyceride), glycerol would not be had so during alcoholysis reaction to generate, react by-product
Thing is only single moisture, can make the moisture on-line of generation using gentle online dehydration technique
Remove, so that reaction is constantly carried out toward positive reaction direction, until fatty acid is fully converted to
Fatty acid short-chain ester.This technique goes for various oils and fatss, the separation of subsequent product
Purification is convenient and easy, has extraordinary industrial applications prospect.
Brief description
Fig. 1 is the technological process that in section Example of the present invention, two-step method prepares fatty acid short-chain ester
Figure.
Specific embodiment
Following examples are used for the present invention is described, but are not limited to the scope of the present invention.If not
Specialize, the routine that in embodiment, technological means used are well known to those skilled in the art
Means, raw materials used are commercial goods.
The technique that embodiment 1 two-step method prepares fatty acid short-chain ester
By 10g Oleum Brassicae campestriss, the water based on oil quality 50%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.200 DEG C of temperature control, 2.5mpa, after reacting 6 hours, effectively oil
The conversion ratio of fat to fatty acid is 99%, is then demultiplex out c8-c24 fatty acid.The fat isolated
Fat acid is for second stage enzyme reactor (equipped with based on 500 standard enzyme activity of unit oil quality
The Digestive Enzyme from aspergillus oryzae aspergillus oryzae), enzyme reactor side connect anhydrous
Methanol tank, opposite side connects vacuum pump and condenser, and the vacuum in control system is 10mpa,
Condenser temperature is 10 DEG C, and temperature of reactor is 20 DEG C, and methanol tank temperature is 25 DEG C, reacts 5
Hour, in system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.4%.
The technique that embodiment 2 two-step method prepares fatty acid short-chain ester
By 10g hogwash fat, the water based on oil quality 100%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.210 DEG C of temperature control, 2.8mpa, after reacting 3 hours, effectively oil
The conversion ratio of fat to fatty acid is 98.5%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid is used for second stage enzyme reactor (equipped with based on 400 standard enzyme of unit oil quality
The Digestive Enzyme from aspergillus oryzae lived), enzyme reactor side connects absolute methanol tank, another
Side connects vacuum pump and condenser, and the vacuum in control system is 20mpa, and condenser temperature is
10 DEG C, temperature of reactor is 25 DEG C, and methanol tank temperature is 30 DEG C, reacts 6 hours, in system
The conversion ratio of fatty acid to fatty acid short-chain ester is 99.5%.
The technique that embodiment 3 two-step method prepares fatty acid short-chain ester
By 10g curcas oil, the water based on oil quality 200%, it is placed in and is suitable to one or more levels
Carry out the hydrolysis of oils and fatss in reactor.230 DEG C of temperature control, 2.8mpa, after reacting 4 hours, effectively
The conversion ratio of oils and fatss to fatty acid is 99%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid is used for second stage enzyme reactor (equipped with based on 500 standard enzyme of unit oil quality
The Digestive Enzyme from antarctic candida candida antarctica lived), enzyme reactor one
Side connects absolute methanol tank, and opposite side connects vacuum pump and condenser, the vacuum in control system
For 80mpa, condenser temperature is 14 DEG C, and enzyme reactor temperature is 30 DEG C, and methanol tank temperature is
25 DEG C, react 5 hours, in system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.6%.
The technique that embodiment 4 two-step method prepares fatty acid short-chain ester
By 10g fiber crops fish oil, the water based on oil quality 400%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.160 DEG C of temperature control, 2.8mpa, after reacting 3 hours, effectively oil
The conversion ratio of fat to fatty acid is 98.8%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid is used for second stage enzyme reactor (equipped with based on 500 standard enzyme of unit oil quality
The Digestive Enzyme from rhizomucor miehei rhizomucor miehei lived), enzyme reactor side
Connect absolute methanol tank, the vacuum that opposite side connects in vacuum pump and condenser control system is
10mpa, condenser temperature is 15 DEG C, and enzyme reactor temperature is 40 DEG C, and methanol tank temperature is 25
DEG C, react 3 hours, in system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.5%.
The technique that embodiment 5 two-step method prepares fatty acid short-chain ester
By 10g acidification oil, the water based on oil quality 400%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.250 DEG C of temperature control, 2.2mpa, after reacting 5 hours, effectively oil
The conversion ratio of fat to fatty acid is 99.5%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid is used for second stage enzyme reactor (equipped with based on 600 standard enzyme of unit oil quality
The Digestive Enzyme from antarctic candida lived), enzyme reactor side connects absolute methanol tank,
Opposite side connects vacuum pump and condenser, and the vacuum in control system is 25mpa, condenser temperature
Spend for 10 DEG C, enzyme reactor temperature is 35 DEG C, methanol tank temperature is 25 DEG C, react 3 hours,
In system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.3%.
The technique that embodiment 6 two-step method prepares fatty acid short-chain ester
By 10g Oleum Ricini, the water based on oil quality 500%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.180 DEG C of temperature control, 2.5mpa, after reacting 3 hours, effectively oil
The conversion ratio of fat to fatty acid is 99.6%, then isolates down c8-c24 fatty acid.Isolate
Fatty acid be used for second stage enzyme reactor (equipped with based on 700 standards of unit oil quality
The Digestive Enzyme from rhizomucor miehei of enzyme activity), enzyme reactor side connects absolute methanol tank,
Opposite side connects vacuum pump and condenser, and the vacuum in control system is 25mpa, condenser temperature
Spend for 10 DEG C, enzyme reactor temperature is 35 DEG C, methanol tank temperature is 25 DEG C, react 4 hours,
In system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.6%.
The technique that embodiment 7 two-step method prepares fatty acid short-chain ester
By 10g waste oil, the water based on oil quality 800%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.190 DEG C of temperature control, 2.59mpa, after reacting 6 hours, effectively
The conversion ratio of oils and fatss to fatty acid is 99.7%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid be used for second stage enzyme reactor (equipped with based on 700 standards of unit oil quality
The Digestive Enzyme from rhizomucor miehei of enzyme activity), enzyme reactor side connects absolute methanol tank,
Opposite side connects vacuum pump and condenser, and the vacuum in control system is 10mpa, condenser temperature
Spend for 12 DEG C, enzyme reactor temperature is 30 DEG C, methanol tank temperature is 25 DEG C, react 4 hours,
In system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.5%.
The technique that embodiment 8 two-step method prepares fatty acid short-chain ester
By 10g microalgae grease, the water based on oil quality 1000%, it is placed in and is suitable to one-level or many
Carry out the hydrolysis of oils and fatss in stage reactor.200 DEG C of temperature control, 2.5mpa, after reacting 4 hours, have
The conversion ratio of effect oils and fatss to fatty acid is 99.6%, is then demultiplex out c8-c24 fatty acid.Separate
The fatty acid going out is used for second stage enzyme reactor (equipped with based on 200 marks of unit oil quality
The Digestive Enzyme from antarctic candida of quasi- enzyme activity and be based on unit oil quality 300
The Digestive Enzyme from rhizomucor miehei of standard enzyme activity), enzyme reactor side connects no water beetle
Alcohol tank, opposite side connects vacuum pump and condenser, and the vacuum in control system is 50mpa, cold
Condenser temperature is 15 DEG C, and enzyme reactor temperature is 40 DEG C, and methanol tank temperature is 30 DEG C, reacts 4
Hour, in system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.5%.
The technique that embodiment 9 two-step method prepares fatty acid short-chain ester
By 10g Petiolus Trachycarpi oil, the water based on oil quality 1000%, it is placed in and is suitable to one or more levels
Carry out the hydrolysis of oils and fatss in reactor.220 DEG C of temperature control, 3.0mpa, after reacting 3 hours, effectively
The conversion ratio of oils and fatss to fatty acid is 99.5%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid be used for second stage enzyme reactor (equipped with based on 300 standards of unit oil quality
The Digestive Enzyme from antarctic candida of enzyme activity and based on unit oil quality 200 mark
The Digestive Enzyme from rhizomucor miehei of quasi- enzyme activity), enzyme reactor side connects absolute methanol
Tank, opposite side connects vacuum pump and condenser, and the vacuum in control system is 60mpa, condensation
Device temperature is 8 DEG C, and immobilized enzyme reactor temperature is 35 DEG C, and Ethanol tank temperature is 30 DEG C, instead
Answer 3 hours, in system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.2%.
The technique that embodiment 10 two-step method prepares fatty acid short-chain ester
By little for 10g Oleum Verniciae fordii, the water based on oil quality 2000%, it is placed in and is suitable to one-level or many
Carry out the hydrolysis of oils and fatss in stage reactor.160 DEG C of temperature control, 3.2mpa, after reacting when 6, effectively
The conversion ratio of oils and fatss to fatty acid is 99.4%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid be used for second stage enzyme reactor (equipped with based on 600 standards of unit oil quality
The Digestive Enzyme from antarctic candida of enzyme activity), enzyme reactor side connects absolute methanol
Tank, opposite side connects vacuum pump and condenser, and the vacuum in control system is 50mpa, condensation
Device temperature is 12 DEG C, and enzyme reactor temperature is 45 DEG C, and methanol tank temperature is 25 DEG C, and reaction 3 is little
When, in system, the conversion ratio of fatty acid to fatty acid short-chain ester is 98%.
The technique that embodiment 11 two-step method prepares fatty acid short-chain ester
By 10g Oleum Brassicae campestriss, the water based on oil quality 100%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.220 DEG C of temperature control, 2.1mpa, after reacting 6 hours, effectively oil
The conversion ratio of fat to fatty acid is 99.4%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid is used for second stage enzyme reactor (equipped with based on 600 standard enzyme of unit oil quality
The Digestive Enzyme from aspergillus oryzae lived), enzyme reactor side connects dehydrated alcohol tank, another
Side connects vacuum pump and condenser, and the vacuum in control system is 10mpa, and condenser temperature is
12 DEG C, temperature of reactor is 30 DEG C, and Ethanol tank temperature is 25 DEG C, reacts 6 hours, in system
The conversion ratio of fatty acid to fatty acid short-chain ester is 99.4%.
The technique that embodiment 12 two-step method prepares fatty acid short-chain ester
By 10g hogwash fat, the water based on oil quality 500%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.220 DEG C of temperature control, 2.8mpa, after reacting 4 hours, effectively oil
The conversion ratio of fat to fatty acid is 99.6%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid is used for second stage enzyme reactor (equipped with based on 600 standard enzyme of unit oil quality
The Digestive Enzyme from aspergillus oryzae lived), enzyme reactor side connects dehydrated alcohol tank, another
Side connects vacuum pump and condenser, and the vacuum in control system is 20mpa, and condenser temperature is
10 DEG C, temperature of reactor is 35 DEG C, and Ethanol tank temperature is 25 DEG C, reacts 7 hours, in system
The conversion ratio of fatty acid to fatty acid short-chain ester is 99.6%.
The technique that embodiment 13 two-step method prepares fatty acid short-chain ester
By 10g curcas oil, the water based on oil quality 500%, it is placed in and is suitable to one or more levels
Carry out the hydrolysis of oils and fatss in reactor.250 DEG C of temperature control, 2.9mpa, after reacting 4 hours, effectively
The conversion ratio of oils and fatss to fatty acid is 99.5%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid be used for second stage enzyme reactor (equipped with based on 800 standards of unit oil quality
The Digestive Enzyme from antarctic candida of enzyme activity), enzyme reactor side connects dehydrated alcohol
Tank, opposite side connects vacuum pump and condenser, and the vacuum in control system is 80mpa, condensation
Device temperature is 14 DEG C, and enzyme reactor temperature is 35 DEG C, and Ethanol tank temperature is 25 DEG C, and reaction 6 is little
When, in system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.7%.
The technique that embodiment 14 two-step method prepares fatty acid short-chain ester
By 10g fiber crops fish oil, the water based on oil quality 1000%, it is placed in and is suitable to one or more levels
Carry out the hydrolysis of oils and fatss in reactor.180 DEG C of temperature control, 3.0mpa, after reacting 3 hours, effectively
The conversion ratio of oils and fatss to fatty acid is 199.8%, is then demultiplex out c8-c24 fatty acid.Separate
The fatty acid going out is used for second stage enzyme reactor (equipped with based on 800 marks of unit oil quality
The Digestive Enzyme from rhizomucor miehei of quasi- enzyme activity), enzyme reactor side connects dehydrated alcohol
Tank, the vacuum that opposite side connects in vacuum pump and condenser control system is 30mpa, condenser
Temperature is 15 DEG C, and enzyme reactor temperature is 40 DEG C, and Ethanol tank temperature is 25 DEG C, reacts 6 hours,
In system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.5%.
The technique that embodiment 15 two-step method prepares fatty acid short-chain ester
By 10g acidification oil, the water based on oil quality 800%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.250 DEG C of temperature control, 3.5mpa, after reacting 2 hours, effectively oil
The conversion ratio of fat to fatty acid is 99.8%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid is used for second stage enzyme reactor (equipped with based on 600 standard enzyme of unit oil quality
The Digestive Enzyme from antarctic candida lived), enzyme reactor side connects dehydrated alcohol tank,
Opposite side connects vacuum pump and condenser, and the vacuum in control system is 25mpa, condenser temperature
Spend for 10 DEG C, enzyme reactor temperature is 35 DEG C, methanol tank temperature is 25 DEG C, react 6 hours,
In system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.5%.
The technique that embodiment 16 two-step method prepares fatty acid short-chain ester
By 10g Oleum Ricini, the water based on oil quality 2000%, it is placed in and is suitable to one or more levels
Carry out the hydrolysis of oils and fatss in reactor.250 DEG C of temperature control, 2.5mpa, after reacting 3 hours, effectively
The conversion ratio of oils and fatss to fatty acid is 99.7%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid be used for second stage enzyme reactor (equipped with based on 700 standards of unit oil quality
The Digestive Enzyme from rhizomucor miehei of enzyme activity), enzyme reactor side connects dehydrated alcohol tank,
Opposite side connects vacuum pump and condenser, and the vacuum in control system is 25mpa, condenser temperature
Spend for 10 DEG C, enzyme reactor temperature is 35 DEG C, Ethanol tank temperature is 25 DEG C, react 8 hours,
In system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.5%.
The technique that embodiment 17 two-step method prepares fatty acid short-chain ester
By 10g waste oil, the water based on oil quality 1000%, it is placed in and is suitable to one or more levels
Carry out the hydrolysis of oils and fatss in reactor.240 DEG C of temperature control, 2.5mpa, after reacting 4 hours, effectively
The conversion ratio of oils and fatss to fatty acid is 99.6%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid be used for second stage enzyme reactor (equipped with based on 900 standards of unit oil quality
The Digestive Enzyme from rhizomucor miehei of enzyme activity), enzyme reactor side connects dehydrated alcohol tank,
Opposite side connects vacuum pump and condenser, and the vacuum in control system is 15mpa, condenser temperature
Spend for 12 DEG C, enzyme reactor temperature is 30 DEG C, Ethanol tank temperature is 25 DEG C, react 6 hours,
In system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.5%.
The technique that embodiment 18 two-step method prepares fatty acid short-chain ester
By 10g yeast oils and fatss, the water based on oil quality 1200%, it is placed in and is suitable to one-level or many
Carry out the hydrolysis of oils and fatss in stage reactor.190 DEG C of temperature control, 2.5mpa, after reacting 4 hours, have
The conversion ratio of effect oils and fatss to fatty acid is 99.6%, is then demultiplex out c8-c24 fatty acid.Separate
The fatty acid going out is used for second stage enzyme reactor (equipped with based on 400 marks of unit oil quality
The Digestive Enzyme from antarctic candida of quasi- enzyme activity and be based on unit oil quality 300
The Digestive Enzyme from rhizomucor miehei of standard enzyme activity), enzyme reactor side connects anhydrous second
Alcohol tank, opposite side connects vacuum pump and condenser, and the vacuum in control system is 30mpa, cold
Condenser temperature is 15 DEG C, and enzyme reactor temperature is 40 DEG C, and Ethanol tank temperature is 30 DEG C, reacts 7
Hour, in system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.2%.
The technique that embodiment 19 two-step method prepares fatty acid short-chain ester
By 10g Petiolus Trachycarpi oil, the water based on oil quality 1000%, it is placed in and is suitable to one or more levels
Carry out the hydrolysis of oils and fatss in reactor.220 DEG C of temperature control, 3.5mpa, after reacting 2 hours, effectively
The conversion ratio of oils and fatss to fatty acid is 99.8%, then isolates down c8-c24 fatty acid.Separate
The fatty acid going out is used for second stage enzyme reactor (equipped with based on 300 marks of unit oil quality
The Digestive Enzyme from antarctic candida of quasi- enzyme activity and be based on unit oil quality 200
The Digestive Enzyme from rhizomucor miehei of standard enzyme activity), enzyme reactor side connects no water beetle
Alcohol tank, opposite side connects vacuum pump and condenser, and the vacuum in control system is 60mpa, cold
Condenser temperature is 8 DEG C, and immobilized enzyme reactor temperature is 35 DEG C, and Ethanol tank temperature is 30 DEG C,
Reaction 8 hours, in system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.2%.
The technique that embodiment 20 two-step method prepares fatty acid short-chain ester
By little for 10g Oleum Verniciae fordii, the water based on oil quality 2000%, it is placed in and is suitable to one-level or many
Carry out the hydrolysis of oils and fatss in stage reactor.150 DEG C of temperature control, 3.5mpa, after reacting 4 hours, have
The conversion ratio of effect oils and fatss to fatty acid is 99.5%, is then demultiplex out c8-c24 fatty acid.Separate
The fatty acid going out is used for second stage enzyme reactor (equipped with based on 800 marks of unit oil quality
The Digestive Enzyme from antarctic candida of quasi- enzyme activity), enzyme reactor side connects no water beetle
Ethanol tank, opposite side connects vacuum pump and condenser, and the vacuum in control system is 50mpa,
Condenser temperature is 12 DEG C, and enzyme reactor temperature is 45 DEG C, and Ethanol tank temperature is 25 DEG C, reaction
6 hours, in system, the conversion ratio of fatty acid to fatty acid short-chain ester was 98%.
The technique that embodiment 21 two-step method prepares fatty acid short-chain ester
By 10g Oleum Brassicae campestriss, the water based on oil quality 100%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.200 DEG C of temperature control, 2.5mpa, after reacting 5 hours, effectively oil
The conversion ratio of fat to fatty acid is 99.3%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid is used for second stage enzyme reactor (equipped with based on 800 standard enzyme of unit oil quality
The Digestive Enzyme from aspergillus oryzae lived), enzyme reactor temperature is 20 DEG C, ethanol and fatty acid
Mol ratio is 5:1, ethanol respectively in reaction 0 hour, 1 hour, 2 hours, 3 hours and 4 little
When each add 1 mole, course of reaction with online dehydration (film or molecular sieve) as shown in Figure 1,
Reaction 4 hours, in system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.4%.
The technique that embodiment 22 two-step method prepares fatty acid short-chain ester
By 10g hogwash fat, the water based on oil quality 100%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.210 DEG C of temperature control, 2.8mpa, after reacting 3 hours, effectively oil
The conversion ratio of fat to fatty acid is 98.5%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid is used for second stage enzyme reactor (equipped with based on 400 standard enzyme of unit oil quality
The Digestive Enzyme from aspergillus oryzae lived), enzyme reactor temperature is 25 DEG C, propanol and fatty acid
Mol ratio be 5:1, alcohol respectively reaction 0 hour, 1 hour, 2 hours, 3 hours and 4 hours
Each add 1 mole, course of reaction with online dehydration (film or molecular sieve) as shown in Figure 1, instead
Answer 3 hours, in system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.5%.
The technique that embodiment 23 two-step method prepares fatty acid short-chain ester
By 10g curcas oil, the water based on oil quality 200%, it is placed in and is suitable to one or more levels
Carry out the hydrolysis of oils and fatss in reactor.230 DEG C of temperature control, 2.8mpa, after reacting 4 hours, effectively
The conversion ratio of oils and fatss to fatty acid is 99%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid is used for second stage enzyme reactor (equipped with based on 500 standard enzyme of unit oil quality
Live the Digestive Enzyme from antarctic candida), enzyme reactor temperature be 35 DEG C, butanol and
Fatty acid mol ratio be 5:1, alcohol respectively reaction 0 hour, 1 hour, 2 hours, 3 hours and
4 hours each to add 1 mole, course of reaction with online dehydration (film or molecular sieve) as shown in Figure 1,
Reaction 4 hours, in system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.6%.
The technique that embodiment 24 two-step method prepares fatty acid short-chain ester
By 10g fiber crops fish oil, the water based on oil quality 400%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.160 DEG C of temperature control, 2.8mpa, after reacting 3 hours, effectively oil
The conversion ratio of fat to fatty acid is 98.8%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid is used for second stage enzyme reactor (equipped with based on 500 standard enzyme of unit oil quality
The Digestive Enzyme from rhizomucor miehei lived), enzyme reactor temperature is 35 DEG C, methanol and fat
Fat acid mol ratio be 5:1, methanol respectively reaction 0 hour, 1 hour, 2 hours, 3 hours and
4 hours each to add 1 mole, course of reaction with online dehydration (film or molecular sieve) as shown in Figure 1,
Reaction 3 hours, in system, the conversion ratio of fatty acid to fatty acid short-chain ester is 99.5%.
The technique that embodiment 25 two-step method prepares fatty acid short-chain ester
By 10g acidification oil, the water based on oil quality 400%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.250 DEG C of temperature control, 2.2mpa, after reacting 5 hours, effectively oil
The conversion ratio of fat to fatty acid is 99.5%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid is used for second stage enzyme reactor (equipped with based on 600 standard enzyme of unit oil quality
Live the Digestive Enzyme from antarctic candida), enzyme reactor temperature be 25 DEG C, methanol and
Fatty acid mol ratio is 4.5:1, and methanol adds 0.5 mole in 0 hour in reaction respectively, at 1 hour,
2 hours, respectively add 1 mole within 3 hours and 4 hours, course of reaction is taken off online with as shown in Figure 1
Water (film or molecular sieve), reacts 3 hours, in system, fatty acid is to the conversion of fatty acid short-chain ester
Rate is 99.3%.
The technique that embodiment 26 two-step method prepares fatty acid short-chain ester
By 10g Oleum Ricini, the water based on oil quality 500%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.180 DEG C of temperature control, 2.5mpa, after reacting 3 hours, effectively oil
The conversion ratio of fat to fatty acid is 99.6%, then isolates down c8-c24 fatty acid.Isolate
Fatty acid be used for second stage enzyme reactor (equipped with based on 700 standards of unit oil quality
The Digestive Enzyme from rhizomucor miehei of enzyme activity), enzyme reactor temperature be 30 DEG C, propanol and
Fatty acid mol ratio is 4.5:1, and alcohol adds 0.5 mole in 0 hour in reaction respectively, at 1 hour,
2 hours, respectively add 1 mole within 3 hours and 4 hours, course of reaction is taken off online with as shown in Figure 1
Water (film or molecular sieve), reacts 4 hours, in system, fatty acid is to the conversion of fatty acid short-chain ester
Rate is 99.6%.
The technique that embodiment 27 two-step method prepares fatty acid short-chain ester
By 10g waste oil, the water based on oil quality 800%, it is placed in that to be suitable to one or more levels anti-
Answer the hydrolysis carrying out oils and fatss in device.190 DEG C of temperature control, 2.59mpa, after reacting 6 hours, effectively
The conversion ratio of oils and fatss to fatty acid is 99.7%, is then demultiplex out c8-c24 fatty acid.Isolate
Fatty acid be used for second stage enzyme reactor (equipped with based on 700 standards of unit oil quality
The Digestive Enzyme from rhizomucor miehei of enzyme activity), enzyme reactor temperature be 25 DEG C, butanol and
Fatty acid mol ratio is 4.5:1, and alcohol adds 0.5 mole in 0 hour in reaction respectively, at 1 hour,
2 hours, respectively add 1 mole within 3 hours and 4 hours, course of reaction is taken off online with as shown in Figure 1
Water (film or molecular sieve), reacts 6 hours, in system, fatty acid is to the conversion of fatty acid short-chain ester
Rate is 99.5%.
The technique that embodiment 28 two-step method prepares fatty acid short-chain ester
By 10g hogwash fat, reclaim the whole heavy phase obtaining in embodiment 27, be placed in and be suitable to one-level
Or in multistage reactor, carry out the hydrolysis of oils and fatss.120 DEG C of temperature control, 1.59mpa, reacts 6 hours
Afterwards, the conversion ratio of effective oils and fatss to fatty acid is 99.7%, is then demultiplex out c8-c24 fatty acid.
The fatty acid isolated is used for second stage enzyme reactor (equipped with based on unit oil quality 700
The Digestive Enzyme from rhizomucor miehei of individual standard enzyme activity), enzyme reactor temperature is 25 DEG C,
Methanol and fatty acid mol ratio are 4.5:1, and methanol adds 0.5 mole in 0 hour in reaction respectively,
At 1 hour, 2 hours, respectively add 1 mole within 3 hours and 4 hours, course of reaction is with as shown in Figure 1
Online dehydration (film or molecular sieve), react 4 hours, in system, fatty acid is to fatty acid short chain
The conversion ratio of ester is 99.5%.
The technique that embodiment 29 two-step method prepares fatty acid short-chain ester
The heavy phase having obtained after having hydrolyzed in 10g hogwash fat, embodiment 26, is placed in and is suitable to one-level
Or in multistage reactor, carry out the hydrolysis of oils and fatss.180 DEG C of temperature control, 1.8mpa, after reacting 5 hours,
The conversion ratio of effectively oils and fatss to fatty acid is 99.7%, is then demultiplex out c8-c24 fatty acid.Point
The fatty acid separating out is used for second stage enzyme reactor (equipped with based on unit oil quality 700
The Digestive Enzyme from rhizomucor miehei of standard enzyme activity), enzyme reactor temperature is 25 DEG C, first
Alcohol and fatty acid mol ratio are 4.5:1, and methanol adds 0.5 mole in 0 hour in reaction respectively, 1
Hour, 2 hours, 1 mole of each addition in 3 hours and 4 hours, course of reaction is with as shown in Figure 1
Online dehydration (film or molecular sieve), reacts 4 hours, in system, fatty acid is to fatty acid short-chain ester
Conversion ratio be 99.5%.
Although, above with a general description of the specific embodiments the present invention has been made in detail
Most description, but on the basis of the present invention, it can be made some modifications or improvements, this is to this
It is obvious for skilled person.Therefore, on the basis without departing from spirit of the present invention
Upper these modifications or improvements, belong to the scope of protection of present invention.
Claims (10)
1. two-step method prepares the technique of fatty acid short-chain ester it is characterised in that including following walking
Rapid:
Step one: grease hydrolysis are become fatty acid, and isolates c8-c24 from hydrolyzate
Fatty acid；
Step 2: with lipase-catalyzed c8-c24 fatty acid, alcoholysis reaction occurs, in enzymatic alcoholysis
In course of reaction, by controlling short-chain alcohol streams to add and carrying out online dehydration, eliminate water byproduct pair
Digestive Enzyme and the impact of efficiency of pcr product, realize the conversion from fatty acid to fatty acid short-chain ester.
2. preparation technology according to claim 1 is it is characterised in that hydrolyze in step one
Reaction is directed in one or more levels reactor intermittently or is continuously added to oils and fatss and is based on oils and fatss matter
The water of amount 50-1200% carries out the hydrolysis of oils and fatss, hydrolysis at 160-230 DEG C, 1.5-3mpa
Under carry out.
3. preparation technology according to claim 1 is it is characterised in that hydrolyze in step one
Heavy phase after finishing separates together, multiple reuse.
4. preparation technology according to claim 1 it is characterised in that step 2 be by
C8-c24 fatty acid and the dress of the Digestive Enzyme based on unit 200-1000 enzyme-activity unit of oil quality
Enter in one or more levels circulation flow reactor, by lipase-catalyzed c8-c24 fatty acid and short chain alcohol
There is esterification, temperature of reactor controls at 20-50 DEG C, c8-c24 fatty acid and short chain alcohol
Mol ratio be 1:4-5, described short chain alcohol is methanol, ethanol, propanol or butanol.
5. preparation technology according to claim 1 is it is characterised in that step 2 enzymatic alcohol
In solution course of reaction, carry out non-uniform flow and add short chain alcohol and online dehydration.
6. preparation technology according to claim 5 is it is characterised in that described non-uniform flow adds
Short chain alcohol refer to reaction 0 hour, 1 hour, 2 hours, 3 hours and 3.5 hours, respectively plus
Enter the short chain alcohol of oils and fatss equimolar amountss.
7. preparation technology according to claim 1 is it is characterised in that described online dehydration
Refer to using film, molecular sieve or short chain alcohol air stripping.
8. preparation technology according to claim 7 is it is characterised in that described film is inorganic
Film, organic membrane or metal film；Described molecular sieve isMolecular sieve；Described short chain alcohol air stripping
It is that reactor side is directly connected with the tank body equipped with anhydrous short chain alcohol, the temperature of anhydrous short chain alcohol
Spend for 20-40 DEG C, the opposite side of reactor is connected with vacuum pump, then vacuum pump and condenser
Connect, by vacuum control in reactor in 10-100mpa, condenser temperature is 5-15 DEG C.
9. the preparation technology according to any one of claim 1-8 is it is characterised in that described
Digestive Enzyme includes the Digestive Enzyme from yeast, mycete, antibacterial or other microorganism；Digestive Enzyme
Combination for single Digestive Enzyme or multiple Digestive Enzyme.
10. the preparation technology according to any one of claim 1-8 is it is characterised in that institute
State oils and fatss be bio-oil, including Vegetable oil lipoprotein, animal oil, waste edible oil, acidification oil,
The concise leftover bits and pieces of oils and fatss and microbial grease；
Wherein, described Vegetable oil lipoprotein includes Oleum Ricini, Oleum Brassicae campestriss, soybean oil, Oleum Arachidis hypogaeae semen, jade
Miyou, Oleum Gossypii semen, Testa oryzae oil, curcas oil, shinyleaf yellowhorn oil, Jatropha curcas oil；Described animal
Oils and fatss include fish oil, Adeps Sus domestica；Described microbial grease includes yeast oils and fatss, microalgae quasi-grease.
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| CN1580218A (en) * | 2003-08-06 | 2005-02-16 | 重庆正和生物能源有限公司 | Method for preparing short-chain aliphatic ester by continuous process using animal-plant oil as raw material |
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| CN1580218A (en) * | 2003-08-06 | 2005-02-16 | 重庆正和生物能源有限公司 | Method for preparing short-chain aliphatic ester by continuous process using animal-plant oil as raw material |
| CN1995287A (en) * | 2006-12-28 | 2007-07-11 | 浙江大学 | Method for preparing biodiesel oil |
| CN101284998A (en) * | 2008-05-06 | 2008-10-15 | 西北大学 | Process for preparing biodiesel by coupling catalytic reaction and separation process |
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