CN102335615B - Oil and fat hydrogenation catalyst for preparing hydrogenated oil with low TFA (Trifluoroacetic Acid) content - Google Patents
Oil and fat hydrogenation catalyst for preparing hydrogenated oil with low TFA (Trifluoroacetic Acid) content Download PDFInfo
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- CN102335615B CN102335615B CN 201110200550 CN201110200550A CN102335615B CN 102335615 B CN102335615 B CN 102335615B CN 201110200550 CN201110200550 CN 201110200550 CN 201110200550 A CN201110200550 A CN 201110200550A CN 102335615 B CN102335615 B CN 102335615B
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Abstract
The invention discloses an oil and fat hydrogenation catalyst for preparing hydrogenated oil with low TFA (Trifluoroacetic Acid) content, comprising the following components in percentage by mass: 1-20% of metallic nickel, 1-20% of metallic copper, 0.1-10% of third metal selected from platinum, palladium, rhodium, ruthenium, osmium, iridium, ferrum, cobalt, molybdenum, manganese, chromium, lanthanum, cerium, aluminum or silver and the balance of diatomite or active carbon. The catalyst is prepared by using a conventional precipitation method. The invention has the advantages that the third metal is introduced on the basis of a supported catalyst taking the nickel as a main catalyst and the copper as a cocatalyst, the allocation proportion of metal crystal forms in a compound catalyst is changed due to the introduction of the third metal element, so that more crystal lattices with catalytic activity are exposed, the catalysis effect is remarkably improved, and the main investigation targets are as follows: the iodine value of hydrogenated oil ranges from 70 to 90, and the TFA content in the obtained hydrogenated oil is lower than 30%.
Description
Technical field
The present invention relates to the hydrogenation of edible oil and fat, especially relate to and a kind ofly preparing containing low-antiform unsaturated fat acid lipid catalyst used by HYDROGENATION OF OILS AND FATS.
Background technology
The daily edible grease of people is called triglyceride (fat), be divided into two kinds of saturated and unrighted acids, and unrighted acid has cis and trans two kinds of configurations.Wherein, trans unrighted acid (TFA) comprises cholesterol trans-fatty acid and how unsaturated trans-fatty acid, the respectively corresponding one or more unconjugated pair of key configurations of its chemical constitution.Two keys in natural acid mostly are cis, and hydrogen atom is positioned at the homonymy of double-linked carbon, and two hydrogen atoms of trans double bond are positioned at the both sides of carbochain.Although the trans unrighted acid of TFA() belong to unrighted acid, the existence of the trans double bond steric configuration of aliphatic acid is produced very large variation, fatty acid molecule is rigid structure, and character approaches saturated fatty acid; And the change of space structure makes the physicochemical property of TFA that great variation also occur, be fusing point the most significantly.The fusing point of general TFA is far above cis fatty acid, as the fusing point of oleic acid is 13.5 ℃, become liquid oily under room temperature, and the fusing point of antiform oleic acid is 46.5 ℃, becomes solid-state smectic under room temperature.Some characteristics that TFA shows are between saturated fatty acid and cis fatty acid.
TFA mainly produces in Content in Hydrogenated Edible Oils, through artificial catalysis, to take unrighted acid appropriateness introducing hydrogen molecule in main vegetable oil, just liquid unrighted acid can be become to the saturated fatty acid easily solidified, thereby the semisolid that vegetable oil is become as butter is even solid-state.Wherein, " transformation of configuration " occurred in some residue unrighted acid, from natural " cis " structure alienation, becomes " trans " structure.HYDROGENATION OF OILS AND FATS, can improve the saturation degree of grease on the one hand, thereby improve the oxidation stability of grease, on the other hand by controlling and changing the hydrogenated oil and fat that hydrogenation technique condition and the saturated degree of hydrogenation are prepared various physical property, as, make grease show shortening, caseation and the physical property such as plastic in food processing process, thereby make it there is purposes widely.Margarine, salad oil, shortening wet goods are all hydrogenation converted products of edible oil and fat.At present, hydrogenated oil and fat be widely used in cure, in the food industry such as leisure, fast food, candy are chocolate, cold drink and quick-frozen.
Although hydrogenated oil and fat has important function at aspects such as the taste of the antioxidative stabilizer that improves grease and change food, local flavors, all contains the TFA of some in hydrogenated oil and fat.Research shows, TFA has damaging effect to health, is mainly manifested in: increase the danger of suffering from angiocardiopathy; Increase the danger of suffering from diabetes; The shortage that causes necessary aliphatic acid; Suppress infant growth.In recent years, the TFA in grease had caused the concern of countries in the world, and American-European countries has proposed the highest requirement of limiting the quantity of and maybe should identify of oneself one after another to its intake.Denmark is the country the earliest absorption of TFA limited, and requires to be no more than 2%, and Australia requires below 3%, and France requires below 3.8%, and Holland and Sweden are below 5%, and the America & Canada requirement is identified the content of TFA.Therefore, how to reduce the content of TFA in food and seem particularly important.
Generally speaking, strictly control grease partial hydrogenation reaction condition, reduce reaction temperature, improve reaction pressure, increase the stir speed (S.S.) of reaction system and reduce catalyst amount, can obtain low TFA product.In addition, adopt noble metal (as palladium, platinum) as catalyst, or adopt homogeneous catalyst, hydrogenation process add 4% alcohol compound (
n-butanols, sorbierite etc.), the additive of some nitrogen compounds such as free fatty, inorganic phosphate, amino acid, urea, amine, adopt hydrazine former as hydrogen, all can reduce the formation of TFA in hydrogenation process with electrochemistry hydrogenation or supercritical fluid hydrogenation etc.
Usually, with traditional hydrogenation catalyst, grease is carried out to hydrogenation, the trans unsaturated fatty acid content of gained hydrogenated oil and fat product is 30～50%.
Summary of the invention
The object of the present invention is to provide a kind of oil hydrogenation catalyst that low TFA levels of hydrogen carburetion is used for preparing, while using this catalyst hydrogenated oil and fat, the TFA content of products obtained therefrom is lower than 30%.
For achieving the above object, the present invention can take following technical proposals:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, comprise feed metal nickel, metallic copper, diatomite or active carbon, it also comprises the third metal, and described the third metal is platinum, palladium, rhodium, ruthenium, osmium, iridium, iron, cobalt, molybdenum, manganese, chromium, lanthanum, cerium, aluminium or silver; The quality per distribution ratio of described raw material is: nickel 1～20%; Copper 1～20%; The third metal is 0.1～10%; Surplus is diatomite or active carbon.
As preferred implementation method, the quality per distribution ratio of described raw material is: nickel 5～15%; Copper 2～10%; The third metal is 0.1～2%; Surplus is diatomite or active carbon.
As best implementation method, the quality per distribution ratio of described raw material is: nickel 10%; Copper 8%; The third metal is 0.5～0.8%; Surplus is diatomite or active carbon.
Oil hydrogenation catalyst of the present invention is prepared according to the conventional precipitation method, utilizes precipitation reaction, and tested component is converted to the indissoluble thing, with precipitation form, from solution, separates.Its operating procedure is: sampling (normally soluble-salt) → (precipitating reagent commonly used has carbonate as Na to dissolve (solvent is generally deionized water) → add precipitating reagent generation precipitation
2cO
3deng, bases as ammoniacal liquor etc.) → filter → washing (water is washed sediment usually, removes the soluble impurity ion) → drying.
The invention has the advantages that and take on the basis of the loaded catalyst that nickel is co-catalyst as major catalyst, copper, introduce the third metal, the introducing of the third metallic element has changed the allocation proportion of metal crystal formation in the composite catalyst, the lattice that more has catalytic activity is revealed, catalytic effect significantly improves, the main index of investigating is: in hydrogenated oil and fat iodine number 70～90 scopes, in the gained hydrogenated oil and fat, the content of TFA is lower than 30%.
Simultaneously; while adopting conventional precipitation method to prepare hydrogenation catalyst; though drying; usually also need catalyst is carried out to the high-temperature roasting processing; obtain the metal oxide of catalyst activity component; then before use catalyst is reduced to processing, obtain having the metallic state of hydrogenation activity, and then carry out hydrogenation.After catalyst drying of the present invention, without carrying out high-temperature roasting, directly the form with carbonate is used for hydrogenation, and logical hydrogen back reduction limit hydrogenation, used convenient.
The specific embodiment
Embodiment 1:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, the nickel that its raw material is quality 10%, 8% copper, 0.5% palladium, surplus is diatomite (catalyst consists of 10%Ni-8%Cu-0.5% palladium/diatomite).
The preparation method of oil hydrogenation catalyst of the present invention is: the CuSO that takes respectively 15.7g
45H
2ni (the NO of O and 24.8g
3)
26H
2o, dissolve with distilled water; Take the PdCl of 0.4g
2, use diluted hydrochloric acid dissolution; The diatomite that takes 32g is placed in beaker, and adds appropriate distilled water, with the magnetic stirring apparatus stirring that heats up, when temperature is raised to 50
oduring C, add other three kinds of solution that prepare in advance, 50
oc constant temperature stirs 1h; Afterwards, drip saturated sodium carbonate solution in this liquid state mixed system, and be added dropwise to complete in 5min, control the pH value between 8～9, continue to stir 2h, then 50
ostanding 3h under C, suction filtration, and be washed with distilled water to neutrality, in vacuum drying chamber 60
othe dry 3h of C, vacuum is 0.09MPa; After dry, solid is worn into and is less than the 100 purpose fine powders catalyst that gets product.
During hydrogenated oil and fat, autoclave is preheating to 180 ℃, then takes soybean oil (or other edible oil and fat) and above-mentioned catalyst and put into together autoclave, wherein the consumption of catalyst is grease amount 0.4%.By the autoclave sealing, with after air in hydrogen exchange still 3-5 time, hydrogen pressure is elevated to 0.5MPa, start agitating device, mixing speed 150r/min, faced H-H reaction at 180 ℃.Sampling in every 20 minutes once, is measured hydrogenated oil and fat sample iodine number, and the hydrogenated oil and fat sample that is 79 to iodine number is further done the TFA content detection, and result shows, in this hydrogenated oil and fat sample, the content of TFA is 23.7%.
Embodiment 2:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, the nickel that its raw material is quality 10%, 8% copper, 0.8% silver, surplus is diatomite (catalyst consists of 10%Ni-8%Cu-0.8%Ag/ diatomite).
The preparation method is with embodiment 1.
Above-mentioned catalyst is applied to the hydrogenation of edible oil and fat, reaction condition is with embodiment 1, the hydrogenated oil and fat sample that to obtain iodine number be 83, and TFA content detection result is 26.4%.
Embodiment 3:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, the nickel that its raw material is quality 10%, 8% copper, 0.8% cerium, surplus is diatomite (catalyst consists of 10%Ni-8%Cu-0.8%Ce/ diatomite).
The preparation method is with embodiment 1.
Above-mentioned catalyst is applied to the hydrogenation of edible oil and fat, reaction condition is with embodiment 1, the hydrogenated oil and fat sample that to obtain iodine number be 87, and TFA content detection result is 29.1%.
Embodiment 4:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, the nickel that its raw material is quality 10%, 8% copper, 0.5% palladium, surplus is active carbon (catalyst consists of the 10%Ni-8%Cu-0.5%Pd/ active carbon).
The preparation method is with embodiment 1.
Above-mentioned catalyst is applied to the hydrogenation of edible oil and fat, reaction condition is with embodiment 1, the hydrogenated oil and fat sample that to obtain iodine number be 73, and TFA content detection result is 19.7%.
Embodiment 5:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, the nickel that its raw material is quality 10%, 8% copper, 0.8% ruthenium, surplus is active carbon (catalyst consists of the 10%Ni-8%Cu-0.8%Ru/ active carbon).
The preparation method is with embodiment 1.
Above-mentioned catalyst is applied to the hydrogenation of edible oil and fat, reaction condition is with embodiment 1, the hydrogenated oil and fat sample that to obtain iodine number be 81, and TFA content detection result is 21.4%.
Embodiment 6:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, the nickel that its raw material is quality 5%, 8% copper, 0.5% palladium, surplus is active carbon (catalyst consists of the 5%Ni-8%Cu-0.5%Pd/ active carbon).
The preparation method is with embodiment 1.
Above-mentioned catalyst is applied to the hydrogenation of edible oil and fat, reaction condition is with embodiment 1, the hydrogenated oil and fat sample that to obtain iodine number be 86, and TFA content detection result is 29.5%
.
Embodiment 7:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, the nickel that its raw material is quality 15%, 8% copper, 0.5% palladium, surplus is active carbon (catalyst consists of the 15%Ni-8%Cu-0.5%Pd/ active carbon).
The preparation method is with embodiment 1.
Above-mentioned catalyst is applied to the hydrogenation of edible oil and fat, reaction condition is with embodiment 1, the hydrogenated oil and fat sample that to obtain iodine number be 72, and TFA content detection result is 24.1%.
Embodiment 8:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, the nickel that its raw material is quality 10%, 2% copper, 0.5% palladium, surplus is active carbon (catalyst consists of the 10%Ni-2%Cu-0.5%Pd/ active carbon).
The preparation method is with embodiment 1.
Above-mentioned catalyst is applied to the hydrogenation of edible oil and fat, reaction condition is with embodiment 1, the hydrogenated oil and fat sample that to obtain iodine number be 88, and TFA content detection result is 28.4%.
Embodiment 9:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, the nickel that its raw material is quality 10%, 5% copper, 0.5% palladium, surplus is active carbon (catalyst consists of the 10%Ni-5%Cu-0.5%Pd/ active carbon).
The preparation method is with embodiment 1.
Above-mentioned catalyst is applied to the hydrogenation of edible oil and fat, reaction condition is with embodiment 1, the hydrogenated oil and fat sample that to obtain iodine number be 80, and TFA content detection result is 23.2%.
Embodiment 10:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, the nickel that its raw material is quality 10%, 10% copper, 0.5% palladium, surplus is active carbon (catalyst consists of the 10%Ni-10%Cu-0.5%Pd/ active carbon).
The preparation method is with embodiment 1.
Above-mentioned catalyst is applied to the hydrogenation of edible oil and fat, reaction condition is with embodiment 1, the hydrogenated oil and fat sample that to obtain iodine number be 84, and TFA content detection result is 25.6%.
Embodiment 11:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, the nickel that its raw material is quality 10%, 8% copper, 0.1% palladium, surplus is active carbon (catalyst consists of the 10%Ni-8%Cu-0.1%Pd/ active carbon).
The preparation method is with embodiment 1.
Above-mentioned catalyst is applied to the hydrogenation of edible oil and fat, reaction condition is with embodiment 1, the hydrogenated oil and fat sample that to obtain iodine number be 76, and TFA content detection result is 21.5%.
Embodiment 12:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, the nickel that its raw material is quality 10%, 8% copper, 1% palladium, surplus is active carbon (catalyst consists of the 10%Ni-8%Cu-1%Pd/ active carbon).
The preparation method is with embodiment 1.
Above-mentioned catalyst is applied to the hydrogenation of edible oil and fat, reaction condition is with embodiment 1, the hydrogenated oil and fat sample that to obtain iodine number be 78, and TFA content detection result is 17.4%.
Embodiment 13:
The oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation of the present invention is used, the nickel that its raw material is quality 10%, 8% copper, 2% palladium, surplus is active carbon (catalyst consists of the 10%Ni-8%Cu-2%Pd/ active carbon).
The preparation method is with embodiment 1.
Above-mentioned catalyst is applied to the hydrogenation of edible oil and fat, reaction condition is with embodiment 1, the hydrogenated oil and fat sample that to obtain iodine number be 80, and TFA content detection result is 18.9%.
Comparative Examples 1:
Consist of 10%Ni-8%Cu/diatomaceous oil hydrogenation catalyst, the identical method preparation according to embodiment 1, under identical reaction condition, the hydrogenated oil and fat sample that to obtain iodine number be 87, TFA content detection result is 47%.
Comparative Examples 2:
Consist of 10%Ni-0.5%Pd/diatomaceous oil hydrogenation catalyst, the identical method preparation according to embodiment 1, under identical reaction condition, the hydrogenated oil and fat sample that to obtain iodine number be 84, TFA content detection result is 43%.
According to above-described embodiment and Comparative Examples, can find out, diatomite or activated carbon supported ternary complex catalyst are compared binary composite catalyst, and in 70-90 iodine number scope, in hydrogenated oil and fat, the content of TFA significantly reduces.
Claims (3)
1. one kind prepares the oil hydrogenation catalyst that low TFA levels of hydrogen carburetion is used, comprise feed metal nickel, metallic copper, diatomite or active carbon, it is characterized in that: it also comprises the third metal, and described the third metal is platinum, palladium, rhodium, ruthenium, osmium, iridium, iron, molybdenum, aluminium or silver; The quality per distribution ratio of described raw material is: nickel 1～20%; Copper 1～20%; The third metal is 0.1～10%; Surplus is diatomite or active carbon.
2. the oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation according to claim 1 is used, it is characterized in that: the quality per distribution ratio of described raw material is: nickel 5～15%; Copper 2～10%; The third metal is 0.1～2%; Surplus is diatomite or active carbon.
3. the oil hydrogenation catalyst that the low TFA levels of hydrogen carburetion of preparation according to claim 2 is used, it is characterized in that: the quality per distribution ratio of described raw material is: nickel 10%; Copper 8%; The third metal is 0.5～0.8%; Surplus is diatomite or active carbon.
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| CN 201110200550 CN102335615B (en) | 2011-07-18 | 2011-07-18 | Oil and fat hydrogenation catalyst for preparing hydrogenated oil with low TFA (Trifluoroacetic Acid) content |
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|---|---|---|---|
| CN 201110200550 CN102335615B (en) | 2011-07-18 | 2011-07-18 | Oil and fat hydrogenation catalyst for preparing hydrogenated oil with low TFA (Trifluoroacetic Acid) content |
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| CN104862083A (en) * | 2015-04-08 | 2015-08-26 | 南昌大学 | Method for reducing content of trans fatty acids in hydrogenated oils and fats |
| CN107088435A (en) * | 2017-04-26 | 2017-08-25 | 东北农业大学 | A kind of preparation method of Ni Pt bimetallic catalysts |
| CN107099383A (en) * | 2017-04-26 | 2017-08-29 | 东北农业大学 | A kind of bimetallic supported catalyst is used for the method for oil with hydrogenated soybean |
| CN107090358A (en) * | 2017-04-26 | 2017-08-25 | 东北农业大学 | A kind of supercritical CO2The method of nickeline magnetic catalyst oil with hydrogenated soybean under state |
| CN108659963B (en) * | 2018-05-25 | 2021-09-21 | 未名生物能源有限公司 | Method for producing biodiesel by using inferior grease as raw material |
| CN114133328A (en) * | 2021-10-22 | 2022-03-04 | 江苏环宇康力科技有限公司 | Production process and formula for preparing monoglyceride from grease |
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