CN109971548A - The preparation method of soap stock and fatty acid calcium - Google Patents
The preparation method of soap stock and fatty acid calcium Download PDFInfo
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- CN109971548A CN109971548A CN201711447113.6A CN201711447113A CN109971548A CN 109971548 A CN109971548 A CN 109971548A CN 201711447113 A CN201711447113 A CN 201711447113A CN 109971548 A CN109971548 A CN 109971548A
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/158—Fatty acids; Fats; Products containing oils or fats
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
- C11B13/02—Recovery of fats, fatty oils or fatty acids from waste materials from soap stock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
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Abstract
The present invention relates to the preparation methods of soap stock and fatty acid calcium.Soap stock preparation method of the invention includes making crude oil and degumming media contact, alkali refining and soap stock separating step, wherein the grease for not separating colloid is directly carried out alkali refining.The present invention prepares fatty acid calcium using thus obtained soap stock, and thus obtained fatty acid calcium can be worth lower than normal plants oil, but growth performance is but rapider than vegetable oil growth, and is powdery granule, it is easier to and feed mixes.
Description
Technical field
The present invention relates to the preparation methods of soap stock and fatty acid calcium.
Background technique
Fat is mainly used for providing energy in feed.It is widely used there are three types of rumen-undegraded fat, respectively high-content
The saturated fatty acid calcium salt of palmitinic acid, higher unsaturated fatty acid and sweet three ester and Long carbon chain.From the perspective of energy, pure palm
The sweet three esters energy of the palmitinic acid and hard fatty acids of acid and high saturation is respectively in 9600kJ or so, and fatty acid calcium energy is only
There is 6600kJ, but the price of fatty acid calcium only has the 2/3 of fatty acid and grease.But the fat directly added in ruminating feed
It does not protect, will be destroyed by ruminant tumor gastric in any form, while interfering the activity of microorganism, reduce cellulose digestion
Rate.Therefore, fatty acid calcium is usually added in ruminating feed.
The preparation method of fatty acid calcium is mainly two kinds at present.One is by fatty acid directly with calcium oxide or hydroxide
The substances such as calcium react；Another kind is to be reacted by sodium hydroxide etc. with grease.
But in existing processing technology, excess alkali is selected to carry out saponification process.In order to ensure that reaction is gone on smoothly, need to add
Enter excessive water to help to react.After the reaction was completed, excess chlorination sodium solution is added to saltout, excessive calcium chloride is then added
Metathesis reaction occurs.Calcium chloride excessive in this way and sodium hydroxide can react generation calcium hydroxide precipitation, encounter in air
Carbon dioxide reacts in turn obtains calcium carbonate.Even if being gone to carry out washing sample with a large amount of water below, a large amount of waste water are not only generated
Environment is polluted, while being also difficult to clean up.
Therefore, there is still a need for a kind of methods of improved production fatty acid calcium for this field.
Summary of the invention
The present invention provides a kind of preparation method of fatty acid calcium, the method includes mixing soap stock and containing the aqueous solution of calcium salt
The step of being reacted, so that fatty acid calcium be prepared；Wherein, the soap stock obtains in the following ways: add alkali to it is de-
Glue medium, which is contacted but do not isolated in the grease of colloid, carries out alkali refining, then separates again and obtains the soap stock.
In one or more embodiments, the soap stock is through supplementing saponification process.
In one or more embodiments, the supplement saponification carries out 2~8 hours at 80~95 DEG C.
In one or more embodiments, after the supplement saponification, the solution containing calcium salt is added and carries out instead
It answers.
In one or more embodiments, the calcium salt is water-soluble Ca salt.
In one or more embodiments, the calcium salt is selected from: calcium chloride, calcirm-fluoride, calcium bromide, calcium iodide, nitric acid
Calcium and calcium gluconate.
In one or more embodiments, before the solution containing calcium salt is added further include be cooled to 45 DEG C it is below
Step.
In one or more technical solutions, the reaction temperature of the reaction is 40-90 DEG C.
In one or more embodiments, in supplement saponification, theoretical base amount that caustic dosage is 80~100%.
In one or more embodiments, theory alkali charge described in supplement saponification calculates as follows:
Wherein, the saponification number of the soap stock is following to calculate:
Wherein, c indicates hydrochloric acid standard solution molar concentration (mol/L)；
V0Indicate that the consumed normal hydrochloric acid of sample holds liquid product (milliliter)；
V indicates that the consumed normal hydrochloric acid of blank holds liquid product (milliliter)；
W indicates sample quality (gram).
In one or more embodiments, theoretical calcium dosage that the additional amount of calcium salt is 95~105%.
In one or more embodiments, the theory calcium dosage calculates as follows:
Wherein, alkali mass unit is gram that alkali quality is theoretical alkali charge.
In one or more embodiments, the soap stock is isolated from natural plants crude oil and animal fat.
In one or more embodiments, the natural plants crude oil is selected from: crude oil of soybean, rapeseed oil crude oil, sunflower
Seed oil crude oil, coconut oil crude oil, peanut oil crude oil, safflower seed oil crude oil, cottonseed oil crude oil, rice bran oil crude oil, corn oil crude oil,
Olive oil crude oil and palm oil crude oil.
The present invention also provides a kind of soap stock preparation methods, which comprises
(1) make crude oil and degumming media contact；
(2) alkali refining, wherein be applied directly to alkali to carry out alkali refining in the grease for not separating colloid of step (1) acquisition；With
(3) separation obtains the soap stock.
In one or more embodiments, the method also includes carrying out supplement saponification to gained soap stock.
In one or more embodiments, in supplement saponification, theoretical base amount that caustic dosage is 80~100%.
In one or more embodiments, theory alkali charge described in supplement saponification calculates as follows:
Wherein, the saponification number of the soap stock is following to calculate:
Wherein, c indicates hydrochloric acid standard solution molar concentration (mol/L)；V0, V respectively indicate blank and the consumed hydrochloric acid of sample
Standard holds liquid product (milliliter)；W indicates sample quality (gram).
The present invention also provides the soap stocks and fatty acid calcium that are prepared using preparation method described herein.
Detailed description of the invention
Fig. 1: the product being prepared using the experimental group 1 of the embodiment of the present invention 1.
Fig. 2: the product being prepared using comparative example 1.
Fig. 3: the product being prepared using comparative example 2.
Specific embodiment
It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention
It can be combined with each other between each technical characteristic of body description, to constitute preferred technical solution.
The conventional technical means for carrying out that saponification process is oil processing field again is centrifuged after fat degumming.But the present invention is sent out
Now, after crude oil and degumming medium come into full contact with, colloid is not isolated, and alkali is directly added to carry out alkali refining, thus isolated soap
Foot is used to prepare fatty acid calcium, can greatly improve conversion ratio.In addition, currently used metathesis reaction prepares fatty acid calcium
Process requirement washing step, thus generate a large amount of waste water.But it is a discovery of the invention that by direct to the grease for not separating colloid
Saponification process stays in system so that the phosphatide in colloid directly alkalizes into phosphorous substance, is saponified to supplement later, is multiple
Decomposition reaction plays the effect for promoting dispersibility, without adding excessive alkali and calcium chloride just can preferably reach reaction end,
And then do not need to wash reaction product, solve the problems, such as metathesis reaction wastewater treatment.
Therefore, the present invention provides a kind of soap stock preparation method, which comprises
(1) make crude oil and degumming media contact；
(2) alkali refining, wherein be applied directly to alkali to carry out alkali refining in the grease for not separating colloid of step (1) acquisition；With
(3) separation obtains the soap stock.
Herein, crude oil refers to come since leaching or squeezing process is by the grease that extracts in plant and animal, including but unlimited
In soybean oil, rapeseed oil, sunflower oil, coconut oil, peanut oil, safflower seed oil, cottonseed oil, rice bran oil, corn oil, olive oil,
The vegetable fat such as palm oil and animal fat.
Herein, degumming medium can be degumming medium commonly used in the art, including but not limited to water, citric acid solution,
Phosphoric acid solution and degummase.Crude oil usually carries out at 50~80 DEG C with degumming media contact, and the time is 10~240 minutes.If
If using degummase, the pH of crude oil and degumming media contact system is generally between 5~6, and the time is in 2~4h.Industrial production
When may suitably adjust pH value to 5~6 with citric acid (NaOH) buffer.
The dosage of degumming medium is usually less than the 0.05wt% of crude oil weight, not higher than the 2wt% of crude oil weight.Water
The usually less than 0.5wt% of crude oil weight, not higher than the 30wt% of crude oil weight, such as 0.5~20wt%, 0.5~
Within the scope of 10wt%, 5~25wt%, the water does not include the water in degumming medium.When degumming medium is acid, with de-
The total weight of glue medium solution, sour concentration are not less than 5wt%.The concentration of acid is normally no higher than 80wt%, for example, can 5~
Within the scope of 65wt%, 10~60wt%, 20~50wt%.
In certain embodiments, degumming medium is water, and the additional amount of water is preferably the 0.5~30% of crude oil weight, example
Such as 2~20%, 2~10%, 2~8%.
Herein, described to refer to crude oil with degumming media contact, it is sufficient to colloid is sufficiently formed in crude oil.
After contact, a certain amount of lye is added in the grease for not separating colloid according to acid value, carries out alkali refining.It can press
Conventional method carries out alkali refining.For example, alkali refining usually 70~95 DEG C at a temperature of carry out, preferably 80~90 DEG C at a temperature of
It carries out.The alkali refining time can be in the range of 30 minutes to 4 hours, such as 1 to 3 hours.Lye can be the common alkali of oil alkali refining
Property solution, is preferably selected from sodium hydroxide solution and potassium hydroxide solution.The concentration of lye is normally no higher than 35wt%.The dosage of alkali
Usually theoretical base amount, this can according to contact after grease obtained acid value be calculated.For example, in certain embodiments
In,
In above formula, AV is the acid value for not separating the grease of colloid, and oily weight is the grease total amount for not separating colloid, the list of oil weight
Position is gram.
After alkali refining, conventional separation method (as being centrifuged) isolated soap stock as described herein can be used.
As the case may be, further saponification can be implemented to gained soap stock (i.e. supplement is saponified).When carrying out supplement saponification,
The saponification number (saponifiable matter ingredient in calibration soap stock) that the soap stock can first be measured, then calculates theoretical caustic dosage again.In certain realities
It applies in scheme, saponification number can calculate as follows:
Wherein:
C indicates hydrochloric acid standard solution molar concentration (mol/L)；
V0Blank is respectively indicated with V and the consumed normal hydrochloric acid of sample holds liquid product (milliliter)；
W indicates sample quality (gram).
Based on the saponification number, the caustic dosage (theoretical base amount) for supplementing saponification can calculate as follows:
In general, supplementing in saponification, the theoretical base amount that caustic dosage is 80~100%.In certain embodiments, caustic dosage
For 85~100% theoretical base amount.In certain embodiments, the theoretical base amount that caustic dosage is 90~100%.
In certain embodiments, if it is very low without sweet three ester or contained sweet three ester content in soap stock, such as less than soap
1%, 0.5%, the 0.1% or lower of foot weight can also be saponified without supplement.
Supplement saponification can 80~95 DEG C at a temperature of carry out, preferably 80~90 DEG C at a temperature of carry out.Supplement saponification
Time can be determined according to real reaction situation, usually in the range of 2~8 hours, such as 4~6 hours.
Therefore, the present invention also includes the soap stock being prepared using the above method, including with after degumming media contact, alkali refining
The soap stock obtained afterwards, and the soap stock further obtained after supplement saponification.In certain embodiments, the soap of soap stock of the invention
Change value is 40-55mg/g, with the total restatement of soap stock, moisture content 40-80%, content of triglyceride 9-30%.
Soap stock as described herein can be used for preparing fatty acid calcium.Therefore, the present invention also provides a kind of preparation of fatty acid calcium
Method, the step of being reacted with the aqueous solution containing calcium salt (metathesis reaction) the method includes mixing soap stock, to prepare
Obtain fatty acid calcium；Wherein, the soap stock obtains in the following ways: add alkali to degumming media contact but do not isolate oil foot
Grease in carry out alkali refining, then separate again and obtain the soap stock.
As it was noted above, further saponification process (supplement is saponified) can be carried out when needing to the soap stock, then again with
Aqueous solution mixing containing calcium salt.After supplement saponification, after solution temperature is down to 45 DEG C or less, is preferably dropped to 40 DEG C or less,
Add the aqueous solution containing calcium salt.Calcium salt can be any water-soluble Ca salt, including but not limited to calcium chloride, calcirm-fluoride, bromination
Calcium, calcium iodide, calcium nitrate and calcium gluconate etc..The mixture of two or more water-soluble Ca salt can be used.Certain
, it is preferable to use one of calcium chloride, calcirm-fluoride, calcium iodide or a variety of in embodiment.In certain embodiments, for big
Soya-bean oil soap stock uses calcirm-fluoride and/or calcium chloride.In certain embodiments, for rapeseed oil soapstock, calcium iodide is used.?
In certain embodiments, for sunflower oil soap stock, calcirm-fluoride is used.In certain embodiments, for cottonseed oil soap stock, make
With one of calcium chloride, calcirm-fluoride, calcium iodide or a variety of.
In general, the temperature of metathesis reaction is 40-90 DEG C, reaction time 0.5-2h.
Theoretical calcium amount can calculate as follows:
In above formula, the unit of alkali quality is gram that alkali quality is theoretical alkali charge.
In general, the theoretical calcium dosage that the additional amount of calcium salt is 95~105%, such as 98~102%.In certain embodiments
In, use theoretical calcium amount.Calcium salt is usually mixed with soap stock in form of an aqueous solutions.The concentration of aqueous solution is normally no higher than
70wt%, such as 10~60wt%.In certain embodiments, it is preferred that the additive amount of aqueous solution is not higher than soap stock weight
20%, such as in the range of 5~15%.
The terminal of metathesis reaction is that essentially all moisture is all adsorbed in fatty acid calcium (water content 50% or so),
Product becomes powdered.Thus fatty acid calcium can be prepared.
In certain embodiments, the method that the present invention prepares fatty acid calcium further includes drying steps.It can be used conventional
Fatty acid calcium of the dry water content of method 50% or so, is down to 5% or less for water content.For example, in certain embodiments
In, it is dried using flashing apparatus, wherein inlet air temperature is set as 100~130 DEG C, and leaving air temp is set as 70~90 DEG C.Wait contain
Water, which is down to 5% or less, can stop drying, and this process about 3~10 minutes.In other embodiments, using fluidized bed and
The drying equipments such as ebullated bed are dried.
The present invention also provides a kind of feed, the feed contains fatty acid calcium as described herein.Fatty acid calcium in feed
Content can be determined according to the different purposes of feed, for example, the content of fatty acid calcium is usually the 0.5- of the feed for chicken feed
5%, such as 1-3%.Part or all of lubricant component used in conventional feed can be replaced with fatty acid calcium of the invention.It changes
Yan Zhi, other ingredients in feed are conventional feed ingredient.
Compared with the conventional method, the invention has the following advantages that
1, can be worth it is lower than normal plants oil, but growth performance but than vegetable oil growth it is rapid；
2, fatty acid calcium is easier as powdery granule and feed mixes.
The present invention will be hereafter illustrated in a manner of specific embodiment.It should be understood that these embodiments are only illustrative, and
The range being not intended to limit the invention.Used calculation method and raw material are as follows in embodiment:
One, calculation method
1, the theoretical caustic dosage of alkali refining step:
In above formula, AV is the acid value for not separating the grease of colloid, and oily weight is the grease total amount for not separating colloid, the list of oil weight
Position is gram.
2, the measurement and calculating (titration is completed) of soap stock saponification number:
C-- hydrochloric acid standard solution molar concentration (mol/L)；
V0, V-- be respectively that the consumed normal hydrochloric acid of blank, sample holds liquid product (milliliter)；
W-is sample weight (gram).
3, the theoretical caustic dosage of supplement saponification
4, theoretical calcium amount
Wherein, the unit of alkali quality be gram, alkali quality is theoretical alkali charge.
Two, raw material
Crude oil of soybean, crude rapeseed oil, sunflower seeds crude oil, crude cotton seed oil are both from Shanghai Jia Li Food Co., Ltd；
DDGS, fish meal, dregs of beans, calcium bicarbonate, mountain flour, premix lead to Witter kind feed corporation,Ltd from Suzhou；
Food-grade lard, soya-bean oil: Shanghai Jia Li Food Co., Ltd；
Feeding lard: Suzhou leads to Witter kind feed corporation,Ltd；
Machine mixer, magnetic force heater: IKA is come from.
Three, detection method
1. the measuring method of acid value is referring to GB 5009.229-2016；
2. Methods of Ether Extract Analysis is referring to GB/T 6433-2006；
3. crude fibre measuring method is referring to GB/T 6434-2006；
4. the measuring method of ash content is referring to GB 5009.4-2016；
5. the measuring method of moisture is referring to GB 5009.3-2016 national food safety standard；
6. crude protein determining method is referring to GB/T 6432-1994 in feed；
7. determining heavy metals GB 5009.74-2014 in food additives.
Embodiment 1
Experimental method is as follows:
1, degumming section
1kg crude oil of soybean, rapeseed oil crude oil, sunflower oil crude oil and cottonseed oil crude oil is respectively taken to pass through filtering and impurity removing respectively
Afterwards, 4% water is added according to crude oil weight, stir about 20min under conditions of 65 DEG C is directly entered lower step alkali refining process.
2, alkali refining section
According to the various crude oil acid values of actual measurement, the sodium hydroxide solution of 20% mass fraction of 3.57 times of acid value amounts is added
(gram), alkali refining 2h under conditions of 80 DEG C after alkali refining, are centrifugally separating to obtain soybean oil soap stock, rapeseed oil soapstock, sunflower respectively
Seed oil soap foot, cottonseed oil soap stock.
Each soap stock index is as shown in table 1 below:
Table 1: the physical parameter of different grease soap stocks
| Soap stock source | Saponification number (mg/g) | Moisture content (%) | Content of triglyceride (%) |
| Soybean oil soap stock | 48 | 54% | 22% |
| Rapeseed oil soapstock | 45 | 48% | 21% |
| Sunflower oil soap stock | 52 | 51% | 18% |
| Cottonseed oil soap stock | 47 | 46% | 28% |
3, supplement saponification
It is saponified experimental group and base amount is as shown in table 2 below.Each experimental group takes the alkali of 2000g soap stock and corresponding amount respectively
(solution for being made into 50%) is put into saponification tank, is warming up to 90 DEG C, is kept stirring state, is cooled to 40 DEG C of left sides after reacting 8h
It is right.
Table 2: the base amount in different soap stock supplement saponification process
4, double decomposition calcification is reacted
The water-soluble Ca salt that separate sources is separately added into the soap stock of each experimental group obtained to step 3 (is configured to 50%
Solution), double decomposition calcification, which is carried out, under the conditions of 50 DEG C reacts 2h, shown in table 3 specific as follows:
Table 3: the metathesis reaction of Different Calcium Sources is added
| Test group # | Soap stock source | Calcium source | Calcium salt additive amount |
| 1 | Soybean oil soap stock | Calcium chloride | Theoretical amount |
| 2 | Soybean oil soap stock | Calcirm-fluoride | 105% theoretical amount |
| 3 | Soybean oil soap stock | Calcium bromide | 95% theoretical amount |
| 4 | Rapeseed oil soapstock | Calcium iodide | Theoretical amount |
| 5 | Rapeseed oil soapstock | Calcium bromide | 105% theoretical amount |
| 6 | Sunflower oil soap stock | Calcirm-fluoride | 95% theoretical amount |
| 7 | Sunflower oil soap stock | Calcium chloride | Theoretical amount |
| 8 | Cottonseed oil soap stock | Calcium iodide | 105% theoretical amount |
| 9 | Cottonseed oil soap stock | Calcium nitrate | 95% theoretical amount |
| 10 | Cottonseed oil soap stock | Calcirm-fluoride+calcium chloride (1:1) | Theoretical amount |
After reaction, without drying, product be moisten it is powdered.
5, dry
Using flashing apparatus, 120 DEG C of inlet air temperature, 80 DEG C of leaving air temp, by product from 50% water content be reduced to 5% with
Under, whole process about 5 minutes.
Composition analysis is carried out to products obtained therefrom, as a result as shown in table 4 below:
Table 4: the physical parameter of fatty acid calcium product
| Index | Crude fat (%) | Ash content (%) | Moisture (%) | Crude protein (%) | Crude fibre (%) |
| Experimental group 1 | 84.50% | 12.10% | 1.70% | 1.30% | 0.40% |
| Experimental group 2 | 87.20% | 9.60% | 1.50% | 1.00% | 0.70% |
| Experimental group 3 | 89.10% | 7.50% | 1.70% | 1.20% | 0.50% |
| Experimental group 4 | 85.50% | 11.10% | 1.60% | 1.40% | 0.40% |
| Experimental group 5 | 87.50% | 9.30% | 1.50% | 1.20% | 0.50% |
| Experimental group 6 | 84.70% | 11.90% | 1.50% | 1.50% | 0.40% |
| Experimental group 7 | 87.80% | 9.00% | 1.00% | 1.50% | 0.70% |
| Experimental group 8 | 84.00% | 13.10% | 1.50% | 2.50% | 0.90% |
| Experimental group 9 | 86.70% | 8.60% | 1.50% | 2.50% | 0.70% |
| Experimental group 10 | 84.50% | 10.60% | 1.30% | 2.70% | 0.70% |
Metal ion detection result after experimental group 1-10 washing is as shown in table 5 below:
Table 5: calcium ion, sodium ions content in different experiments group fatty acid calcium
Conclusion: the purpose of washing is not intended to removal Na salt, because natively needing to add NaCl, water in feed formula
The purpose washed is whether measurement Ca exists in the form of fatty acid calcium, because fatty acid calcium is not soluble in water, and calcium chloride is readily soluble
Yu Shui can directly be washed out if calcium chloride does not participate in reaction by water.Calcium accounting 6.64% in pure fatty acid calcium, because pure
Calcium ion content is 66400ppm in net fatty acid calcium, and experimental group 1 is 61512ppm, and the conversion ratio being thus calculated is
92.6%.
The granularity size of 1 product of experimental group is as shown in table 6 below:
Table 6
| Granularity | Diameter (μm) |
| D90 | 628.22 |
| D10 | 44.9 |
| Average value | 306.1 |
Comparative example 1
Experimental method is as follows:
1, degumming section
It takes 1kg crude oil of soybean after filtering and impurity removing, adds 4% water, 65 DEG C of condition in crude oil according to phosphorus content
Lower stir about 20min, centrifuge enter next section of process after isolating colloid.
2, alkali refining section
The grease for isolating colloid is subjected to next step alkali refining.According to the crude oil of soybean acid value of actual measurement, acid value 3.57 is added
The sodium hydroxide solution (gram) of 20% mass fraction of times amount, alkali refining 2h under conditions of 80 DEG C after alkali refining, are centrifugated
To soap stock.
3, supplement saponification
It takes out the soybean oil soap stock that about 50g step 2 obtains to put into saponification tank, according to the calculation formula of supplement saponification number
The aqueous solution of the sodium hydroxide containing theoretical amount is added, is warming up to 90 DEG C, is kept stirring state, is cooled to 40 DEG C or so after reacting 8h.
4, double decomposition calcification is reacted
Calcium chloride solution (being configured to 50% solution) is added according to theoretical amount in the sample of step 3, carries out double decomposition calcification
Reaction.
5, dry
Using flashing apparatus, 120 DEG C of inlet air temperature, 80 DEG C of leaving air temp, by product from 50% water content be reduced to 5% with
Under, whole process about 5 minutes.Product agglomerates in flash distillation exit, influences material and normally collects.
The metal ion detection result of products obtained therefrom is as shown in table 7 below.
Table 7
| Metal ion | Without washing content (ppm) | Content (ppm) after washing |
| Ca | 62302.2 | 51412.8 |
| Na | 16140.0 | 8640.2 |
| As | 0.31 | - |
| Pb | 0.08 | - |
Conclusion: calcium accounting 6.64% in pure fatty acid calcium, the conversion ratio being thus calculated are 77.4%.Cause to turn
The main reason for rate is low is product agglomeration (Fig. 2), and internal product can not continue to react with calcium chloride, after resulting in washing in this way
Calcium chloride can be washed off, therefore calcium content has a certain amount of reduction after washing, while sodium ion is because many also with fatty acid
The form of sodium is wrapped in the inside, and therefore, it is difficult to wash out.
Comparative example 2
Experimental method is as follows:
1, degumming separates oil foot
Crude oil adds 4% water, stir about 20min under conditions of 65 DEG C, centrifuge after filtering and impurity removing in crude oil
Isolate colloid.
2, the saponification of oil foot
The colloid that a upper process obtains is transferred to the sodium hydroxide that theoretical amount is added in another reactor tank according to saponification number
Solution carries out generation saponification in advance and obtains the saponified of oil foot.Method for saponification is referring to identical as the supplement saponification of embodiment 1
Reaction, wherein caustic dosage applies the caustic dosage formula of supplement saponification, and the saponification number of soap stock in formula is substituted with the saponification number of oil foot,
With the quality of soap stock in oil foot weight substitution formula.
3, double decomposition calcification is reacted
Calcium chloride solution (being configured to 50% solution) is added according to theoretical amount in saponified by oil foot, carries out double decomposition calcification
Reaction.
4, dry
Using flashing apparatus, 120 DEG C of inlet air temperature, 80 DEG C of leaving air temp, by product from 50% water content be reduced to 5% with
Under, whole process about 5 minutes.Product agglomerates in flash distillation exit, influences material and normally collects.
The metal ion detection result of products obtained therefrom is as shown in table 8 below.
Table 8
| Metal ion | Without washing content (ppm) | Content (ppm) after washing |
| Ca | 42302.2 | 33434.8 |
| Na | 18140.0 | 7143.7 |
| As | 0.30 | - |
| Pb | 0.10 | - |
Conclusion: calcium accounting 6.64% in pure fatty acid calcium, the conversion ratio being thus calculated are 50.3%.It causes to turn
The main reason for rate is lower is that product is tacky (Fig. 3), and the content of phospholipid in oil foot is sufficiently high, and the viscosity of phosphatide is very high, is held
Easily alkali and soap is prevented to continue to react.
Comparative example 3
Experimental method is as follows:
1, degumming section
It takes 1kg crude oil of soybean after filtering and impurity removing, 4% water is added in crude oil according to phosphorus content, in 65 DEG C of item
Stir about 20min under part is directly entered lower step process.
2, alkali refining section
According to the crude oil of soybean acid value of actual measurement, the sodium hydroxide solution of 20% mass fraction of 3.57 times of acid value amounts is added
(gram), alkali refining 2h under conditions of 80 DEG C after alkali refining, are centrifugally separating to obtain soap stock.
3, supplement saponification
The soybean oil soap stock for taking 50g step 2 to obtain, for supplement method for saponification with embodiment 1, base amount is theoretical alkali.It completes
50g sodium chloride solution (35% concentration) is added afterwards, and saltout 1h.
4, double decomposition calcification is reacted
Calcium chloride solution (being configured to 50% solution) is added according to theoretical additive amount, metathesis reaction occurs.
5, after dry
Using flashing apparatus, 120 DEG C of inlet air temperature, 80 DEG C of leaving air temp, by product from 50% water content be reduced to 5% with
Under, whole process about 5 minutes.
Product testing after drying the results are shown in Table 9.
Table 9
| Metal ion | Without washing content (ppm) | Content (ppm) after washing |
| Ca | 62302.2 | 45412.8 |
| Na | 26140.0 | 13122.7 |
| As | 0.29 | - |
| Pb | 0.11 | - |
Conclusion: calcium accounting 6.64% in pure fatty acid calcium, the conversion ratio being thus calculated are 68.3%.
Comparative example 4
Experimental method is as follows:
1, degumming section
It takes 1kg crude oil of soybean after filtering and impurity removing, 4% water is added in crude oil according to phosphorus content, in 65 DEG C of item
Stir about 20min under part is directly entered lower step process.
2, alkali refining section
According to the crude oil of soybean acid value of actual measurement, the sodium hydroxide solution of 20% mass fraction of 3.57 times of acid value amounts is added
(gram), alkali refining 2h under conditions of 80 DEG C after alkali refining, are centrifugally separating to obtain soap stock.
3, supplement saponification
The soybean oil soap stock for taking 50g step 2 to obtain, for supplement method for saponification with embodiment 1, base amount is 75% theoretical alkali.
4, double decomposition calcification is reacted
According to the double decomposition calcification reaction condition of embodiment 1, the calcium chloride solution of the theoretical additive amount of addition 95% (is configured to
50% solution) metathesis reaction occurs.
5, dry
Using flashing apparatus, 120 DEG C of inlet air temperature, 80 DEG C of leaving air temp, by product from 50% water content be reduced to 5% with
Under, whole process about 5 minutes.
Product testing after drying the results are shown in Table 10.
Table 10
| Metal ion | Without washing content (ppm) | Content (ppm) after washing |
| Ca | 59101 | 50218 |
| Na | 24140.0 | 12133.7 |
| As | 0.28 | - |
| Pb | 0.11 | - |
Final products are tacky, can not form.
Comparative example 5
Experimental method is as follows:
1, degumming section
It takes 1kg crude oil of soybean after filtering and impurity removing, 4% water is added in crude oil according to phosphorus content, in 65 DEG C of item
Stir about 20min under part is directly entered lower step process.
2, alkali refining section
According to the crude oil of soybean acid value of actual measurement, the sodium hydroxide solution of 20% mass fraction of 3.57 times of acid value amounts is added
(gram), alkali refining 2h under conditions of 80 DEG C after alkali refining, are centrifugally separating to obtain soap stock.
3, supplement saponification
The soybean oil soap stock for taking 50g step 2 to obtain, for supplement method for saponification with embodiment 1, base amount is 120% theoretical alkali.
4, double decomposition calcification is reacted
According to the condition of embodiment 1, the calcium chloride solution (being configured to 50% solution) of the theoretical additive amount of addition 95% occurs
Metathesis reaction.
5, dry
Using flashing apparatus, 120 DEG C of inlet air temperature, 80 DEG C of leaving air temp, by product from 50% water content be reduced to 5% with
Under, whole process about 5 minutes.
Product testing after drying the results are shown in Table 11.
Table 11
| Metal ion | Without washing content (ppm) | Content (ppm) after washing |
| Ca | 65101 | 33218 |
| Na | 26140.0 | 12104 |
| As | 0.33 | - |
| Pb | 0.13 | - |
Conclusion: calcium accounting 6.64% in pure fatty acid calcium, the conversion ratio being thus calculated are 51.5%, alkali number mistake
Greatly, preferentially sodium hydroxide and calcium chloride are reacted, is washed with water wash-off, the calcium of subsequent metathesis reaction after generating calcium hydroxide
Amount is insufficient.
Comparative example 6
Experimental method is as follows:
1, degumming section
It takes 1kg crude oil of soybean after filtering and impurity removing, 4% water is added in crude oil according to phosphorus content, in 65 DEG C of item
Stir about 20min under part is directly entered lower step process.
2, alkali refining section
According to the crude oil of soybean acid value of actual measurement, the sodium hydroxide solution of 20% mass fraction of 3.57 times of acid value amounts is added
(gram), alkali refining 2h under conditions of 80 DEG C after alkali refining, are centrifugally separating to obtain soap stock.
3, supplement saponification
The soybean oil soap stock for taking 50g step 2 to obtain, for supplement method for saponification with embodiment 1, base amount is 90% theoretical alkali.
4, double decomposition calcification is reacted
According to the double decomposition calcification reaction condition of embodiment 1, the calcium chloride solution that 90% theoretical additive amount is added (is configured to
50% solution) metathesis reaction occurs.
5, after dry
Using flashing apparatus, 120 DEG C of inlet air temperature, 80 DEG C of leaving air temp, by product from 50% water content be reduced to 5% with
Under, whole process about 5 minutes.
Product testing after drying the results are shown in Table 12.
Table 12
| Metal ion | Without washing content (ppm) | Content (ppm) after washing |
| Ca | 65101 | 32244 |
| Na | 26140.0 | 12104 |
| As | 0.32 | - |
| Pb | 0.14 | - |
Conclusion: calcium amount is insufficient, reacts hypocalcia.
Comparative example 7
Experimental method is as follows:
1, degumming section
It takes 1kg crude oil of soybean after filtering and impurity removing, 4% water is added in crude oil according to phosphorus content, in 65 DEG C of item
Stir about 20min under part is directly entered lower step process.
2, alkali refining section
According to the crude oil of soybean acid value of actual measurement, the sodium hydroxide solution of 20% mass fraction of 3.57 times of acid value amounts is added
(gram), alkali refining 2h under conditions of 80 DEG C after alkali refining, are centrifugally separating to obtain soap stock.
3, supplement saponification
The soybean oil soap stock for taking 50g step 2 to obtain, for supplement method for saponification with embodiment 1, base amount is 85% theoretical alkali.
4, double decomposition calcification is reacted
According to the double decomposition calcification reaction condition of embodiment 1, the calcium chloride solution (configuration of 110% theoretical additive amount is added
At 50% solution) metathesis reaction occurs.
5, dry
Using flashing apparatus, 120 DEG C of inlet air temperature, 80 DEG C of leaving air temp, by product from 50% water content be reduced to 5% with
Under, whole process about 5 minutes.
Product testing after drying the results are shown in Table 13.
Table 13
| Metal ion | Without washing content (ppm) | Content (ppm) after washing |
| Ca | 65101 | 44634 |
| Na | 26140.0 | 14154 |
| As | 0.31 | - |
| Pb | 0.15 | - |
Conclusion: adding calcium amount excessive, and same excessive calcium causes product to be easy agglomeration.
Test case 1
The experimental group 1,5,6 in embodiment 1, the fatty acid calcium product being prepared in comparative example 1,3, soybean are used respectively
Oil, lard, the combination of lard+soybean oil are as the feed fat source in table 14, according to following feed formula, formula feed.
Table 14
| Feed formula raw material | Weight ratio |
| Corn | 60.2 |
| Fish meal | 2 |
| DDGS | 2 |
| Dregs of beans | 30 |
| Fat source | 1.5 |
| Calcium monohydrogen phosphate | 1.5 |
| Mountain flour | 1.5 |
| Premix | 1.3 |
| It is total | 100 |
Breeding way:
Henhouse is tested, is kept the temperature using electric heater, coal stove pipe, windowing ventilation.Cage cultivation device is the cage of cave body, and 3 layers of overlapping are total
45 cages, every 10 plumage of cage, independent hopper and sink.10 temperature are placed on the upper layer, middle layer, bottom of cage different location respectively
Meter.4 exhaust fans of henhouse.
Experimental group and cultivation situation are as described in Table 15.
Table 15: experimental group and cultivation situation
| 3 weeks chicken weights (g) | 6 weeks chicken weights (g) | 9 weeks chicken weights (g) | |
| Soya-bean oil | 285±45 | 767±124 | 1476±358 |
| Food-grade lard | 287±64 | 795±168 | 1513±412 |
| Feeding lard | 266±79 | 675±205 | 1311±492 |
| Soya-bean oil+food-grade lard | 248±56 | 611±189 | 1227±450 |
| The fatty acid calcium of 1 experimental group 1 of embodiment | 330±73 | 1040±185 | 2014±422 |
| The fatty acid calcium of 1 experimental group 5 of embodiment | 321±45 | 1026±133 | 1985±308 |
| The fatty acid calcium of 1 experimental group 6 of embodiment | 317±58 | 1015±175 | 1998±57 |
| Comparative example 1 | 293±64 | 807±148 | 1333±212 |
| Comparative example 3 | 294±53 | 798±176 | 1498±307 |
As can be seen from the above table, fatty acid calcium product is for grease, although energy provides lower, growth effect
There is no disadvantages for fruit.Simultaneously in refining process, gelatin substance either is eliminated by scouring processes or is saltoutd
Glue class components precipitate is allowed to get off after separation in the process, it is good that effect is not so good as not remove gelatin substance.
Claims (10)
1. a kind of soap stock preparation method, which comprises
(1) make crude oil and degumming media contact；
(2) alkali refining, wherein be applied directly to alkali to carry out alkali refining in the grease for not separating colloid of step (1) acquisition；With
(3) separation obtains the soap stock.
2. the method as described in claim 1, which is characterized in that the method also includes carrying out supplement saponification to gained soap stock
Step；
Preferably, the supplement saponification is to carry out at 80~95 DEG C saponification 2~8 hours；
Preferably, in the supplement saponification, the theoretical base amount that caustic dosage is 80~100%, such as 90~100%, wherein described
Theoretical alkali charge calculates as follows:
Wherein, the saponification number of the soap stock calculates as follows:
Wherein, c indicates hydrochloric acid standard solution molar concentration (mol/L)；V0, V respectively indicates blank and the consumed normal hydrochloric acid of sample holds
Liquid product (milliliter)；W indicates sample quality (gram).
3. the soap stock being prepared using method of any of claims 1 or 2.
4. a kind of preparation method of fatty acid calcium, which is characterized in that the method includes mixing soap stock and containing the aqueous solution of calcium salt
The step of being reacted, so that fatty acid calcium be prepared；Wherein, the soap stock obtains in the following ways: add alkali to it is de-
Glue medium, which is contacted but do not isolated in the grease of colloid, carries out alkali refining, then separates again and obtains the soap stock；Preferably, the soap
Foot is through supplementing saponification process.
5. method as claimed in claim 4, which is characterized in that
The supplement saponification carries out 2~8 hours at 80~95 DEG C；And/or
In the supplement saponification, the theoretical base amount that caustic dosage is 80~100%, such as 90~100%, the theory alkali charge is such as
Lower calculating:
Wherein, the saponification number of the soap stock calculates as follows:
Wherein, c indicates hydrochloric acid standard solution molar concentration (mol/L)；
V0Indicate that the consumed normal hydrochloric acid of sample holds liquid product (milliliter)；
V indicates that the consumed normal hydrochloric acid of blank holds liquid product (milliliter)；
W indicates sample quality (gram).
6. method as described in claim 4 or 5, which is characterized in that
After the supplement saponification, the solution containing calcium salt is added and is reacted, it is preferable that is added described containing the molten of calcium salt
Before liquid reaction, include the steps that temperature is down to 45 DEG C or less；And/or
The calcium salt is water-soluble Ca salt, is preferably selected from: calcium chloride, calcirm-fluoride, calcium bromide, calcium iodide, calcium nitrate and glucose
Sour calcium；And/or
The reaction temperature of the reaction is 40-90 DEG C.
7. the method as described in any one of claim 4-6, which is characterized in that the additional amount of calcium salt is 95~105%, such as
98~102% theoretical calcium dosage, wherein the theory calcium dosage calculates as follows:
Wherein, alkali mass unit is gram that alkali quality is theoretical alkali charge.
8. the method as described in any one of claim 1-2,4-7, which is characterized in that the soap stock is isolated from natural plants
Crude oil and animal fat；Preferably, the natural plants crude oil is selected from: crude oil of soybean, rapeseed oil crude oil, sunflower oil crude oil,
Coconut oil crude oil, peanut oil crude oil, safflower seed oil crude oil, cottonseed oil crude oil, rice bran oil crude oil, corn oil crude oil, olive oil hair
Oil and palm oil crude oil.
9. the fatty acid calcium being prepared using fatty acid calcium preparation method described in any one of claim 4-8.
10. a kind of feed contains fatty acid calcium as claimed in claim 9.
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| CN112680298A (en) * | 2021-01-04 | 2021-04-20 | 广东药科大学 | Tableware detergent and laundry detergent taking soapstock as raw material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB427680A (en) * | 1933-04-28 | 1935-04-29 | Metallgesellschaft Ag | Process for refining vegetable and animal oils and fats |
| CN1192772A (en) * | 1995-08-11 | 1998-09-09 | 海厄姆·迈尔斯咨询有限公司 | Method for refining oils and fats |
| CN1629266A (en) * | 2004-10-13 | 2005-06-22 | 大连市畜牧兽医研究所 | Process for producing fat powder by using oil deposit |
| TW200840863A (en) * | 2007-03-21 | 2008-10-16 | Norel S A | Procedure for producing calcium, sodium or magnesium fatty acid soaps or vegetable or animal soapstocks and their use as nutrients in monogastric animal feeds |
| CN101358160A (en) * | 2007-07-30 | 2009-02-04 | 孙树江 | Separation method of fat and soap stock at normal-temperature |
| CN103333751A (en) * | 2012-12-06 | 2013-10-02 | 三河汇福生物科技有限公司 | Method of producing powdered soap by using vegetable oil alkali refining nigre containing phospholipid |
| CN103571617A (en) * | 2012-07-26 | 2014-02-12 | 丰益(上海)生物技术研发中心有限公司 | Improved animal fat processing technology |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009522241A (en) * | 2005-12-30 | 2009-06-11 | ノレル・ソシエダッド・アノニマ | Method for producing calcium soap for animal feed |
-
2017
- 2017-12-27 CN CN201711447113.6A patent/CN109971548B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB427680A (en) * | 1933-04-28 | 1935-04-29 | Metallgesellschaft Ag | Process for refining vegetable and animal oils and fats |
| CN1192772A (en) * | 1995-08-11 | 1998-09-09 | 海厄姆·迈尔斯咨询有限公司 | Method for refining oils and fats |
| CN1629266A (en) * | 2004-10-13 | 2005-06-22 | 大连市畜牧兽医研究所 | Process for producing fat powder by using oil deposit |
| TW200840863A (en) * | 2007-03-21 | 2008-10-16 | Norel S A | Procedure for producing calcium, sodium or magnesium fatty acid soaps or vegetable or animal soapstocks and their use as nutrients in monogastric animal feeds |
| CN101358160A (en) * | 2007-07-30 | 2009-02-04 | 孙树江 | Separation method of fat and soap stock at normal-temperature |
| CN103571617A (en) * | 2012-07-26 | 2014-02-12 | 丰益(上海)生物技术研发中心有限公司 | Improved animal fat processing technology |
| CN103333751A (en) * | 2012-12-06 | 2013-10-02 | 三河汇福生物科技有限公司 | Method of producing powdered soap by using vegetable oil alkali refining nigre containing phospholipid |
Non-Patent Citations (3)
| Title |
|---|
| ZHANG, H，等: "Mechanism for defoaming by oils and calcium soap in aqueous systems", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| 庄殿忠，等: "《油脂工业企业员工必读》", 31 December 1998, 新疆科技卫生出版社 * |
| 戴晋生: "棉籽油皂脚的综合利用", 《太原科技》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680298A (en) * | 2021-01-04 | 2021-04-20 | 广东药科大学 | Tableware detergent and laundry detergent taking soapstock as raw material and preparation method thereof |
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