CN103657642A - Grease hydrogenation catalyst - Google Patents
Grease hydrogenation catalyst Download PDFInfo
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- CN103657642A CN103657642A CN201310650543.3A CN201310650543A CN103657642A CN 103657642 A CN103657642 A CN 103657642A CN 201310650543 A CN201310650543 A CN 201310650543A CN 103657642 A CN103657642 A CN 103657642A
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Abstract
The invention provides a grease hydrogenation catalyst. Platinum is loaded on ZrO2, forming the grease hydrogenation catalyst; the actual load amount of platinum is 1.79%, and the catalyst has a specific surface area of 32.88 m<2>/g, a specific pore volume of 0.133 cm<3>/g, an average pore size of 16.16 nm and a platinum particle size of 1 +/- 0.25 nm. The catalyst is prepared by using an impregnation reduction method; a solution is prepared from chloroplatinic acid hexahydrate, the solution and a carrier undergo impregnation and stirring for a period of time, then pressure reduction distillation is carried out to remove moisture, drying is carried out, a synthesized solid is calcined and then reduced at a high temperature in hydrogen so as to prepare the catalyst. The invention has the following advantages: the catalyst is simple to prepare, raw materials are widely available, catalytic activity of hydrogenated soybean oil is high, the amount of generated trans-fatty acid is small compared with a nickel catalyst, the catalyst has good selectivity, and the quality of hydrogenated grease is good.
Description
Technical field
The present invention relates to a kind of catalyst.
Background technology
Hydrogenation, as the important modifying process of grease deep processing, can change natural structure and the Triglycerides of grease.Owing to there being many cis unsaturated fatty acids in crude vegetal, in illumination or air, be easily oxidized, become sour, therefore people are added to hydrogen on the unsaturated double-bond of aliphatic acid by hydrogenation, the crude vegetal that makes to be rich in polyunsaturated fatty acid is transformed into take monounsaturated fatty acids as main hydrogenated oil and fat, make molten, the elevation of boiling point of grease, improve the oxidation stability of grease, Shelf-life, plasticity strengthens, and the stink and the local flavor that relax grease are deteriorated.
Edible oil hydrogenation is generally that to take the metals such as reproducibility nickel be catalyst, the process to the unsaturated bond catalytic hydrogenation existing in grease, and resulting grease is called hydrogenated oil and fat.At present in traditional industry the hydrogenated oil and fat of large-scale production mainly to take metallic nickel, copper be catalyst, because nickel catalyst has carcinogenicity, and Cu-series catalyst can produce a large amount of trans-fatty acids, and trace copper exists and can accelerate grease oxidation rancid.And the high temperature of hydrogenation process, high pressure, catalytic condition also can cause a large amount of trans-fatty acid (trans fatty acids) to produce, in different hydrogenated vegetable oils, the content of trans-fatty acid has very big-difference because of the difference of processing technology.
Research shows, TFA can increase the danger that people suffer from angiocardiopathy and type II diabetes, affects upgrowth and development of children, increases risk of cancer etc.Due to health is existed to harm, TFA has become the hot issue that government, academia, food processing industry and the general common people pay close attention to.Lot of domestic and foreign research is all devoted to seek to reduce in hydrogenation process the method for TFA growing amount.By controlling suitable hydroprocessing condition (temperature, pressure, mixing speed), select suitable noble metal catalyst, additive as amine substance, inorganic phosphate, free fatty etc., or adopt the methods such as supercritical fluid hydrogenation and electrochemistry hydrogenation reaction, all can reduce the content of trans-fatty acid in hydrogenated oil and fat.
Summary of the invention
It is active component that the present invention selects the noble metal platinum of high activity, low trans fatty acid generation, is carried on artificial synthetic carrier zirconium dioxide and prepares carried noble metal platinum catalyst.By the hydrogenation of soybean oil, evaluate it for high activity, low trans-fatty acid content, selectively good, active metal component few catalyst that runs off, and observe by the quality of hydrogenated oil and fat, this catalyst is compared commercial nickel catalyst and is more suitable for generation hydrogenated edible oil.
The object of the invention is to be achieved through the following technical solutions:
Oil hydrogenation catalyst: in catalyst, metal platinum content is 1.79% of carrier zirconium dioxide weight, wherein carrier zirconium dioxide ZrO
2specific area be 26.3203 m
2g
-1, aperture is 15.52589 nm, metal platinum spread loads on carrier, granular size 1 ± 0.25 nm.
The preparation method who the invention still further relates to described catalyst, concrete steps are as follows:
(1) carrier ZrO
2preparation: zirconyl nitrate solid is made into the aqueous solution, adds gradually 1 mol/L ammonia spirit until produce sediment; It is centrifugal, and washing is to neutral.Solid 110 ℃ of oven dry, the Muffle furnace that is finally placed in 550 ℃ bakes 5 h;
(2) by the water dissolving at normal temperatures of six hydration chloroplatinic acids, be made into and take vehicle weight as primary standard substance 2% Pt/ZrO
2;
(3) by platinum acid chloride solution and zirconia carrier continuous stirring 16 h at normal temperatures, stir and be placed on evaporated under reduced pressure in Rotary Evaporators;
(4) by synthetic solid transfer to surface plate, in 60 ℃ of vacuum drying, be then placed in 450 ℃ of Muffle furnaces and bake 5 h;
(5) finally the catalyst after roasting is placed in to tube furnace Program and is warming up to 500 ℃ of reduction activation 6 h, the catalyst preparing is used nitrogen-sealed to preserve.
The described reduction activation of step (5) is that logical nitrogen blowing, with the speed temperature programming to 500 ℃ of 10 ℃/min, becomes high-purity hydrogen by nitrogen replacement, reduction activation 6h in the atmosphere that is 30mL/min at hydrogen flow rate in airtight tube furnace.
The catalyst program of using above method to prepare is simple, especially manually the technique of synthetic zirconium dioxide is easy to operate, metal platinum raw material sources are abundant, the activity of synthetic catalyst oil with hydrogenated soybean is high, metal component number of dropouts is few, the content of trans fatty acids low (25.48 g/100g soybean oil) that contrast Raney nickel produces when iodine number 70, selectively good, the stay in grade of hydrogenated oil and fat.
The sign specification of catalyst finished product prepared by the present invention is: platinum actual negative carrying capacity is that 1.79%(be take vehicle weight as benchmark), the specific area of its catalyst (BET) is 32.88 m
2g
-1, specific pore volume is 0.133 cm
3g
-1, average pore size is 16.16 nm, platinum particle size is about 1 ± 0.25 nm.The metallic element platinum that shows load according to XRD collection of illustrative plates respectively in 2 θ=39.78 °, 2 θ=46.26 °, 2 θ=67.48 ° locate to find its 111,200 with 220, illustrate that carrier surface exists without the oxide of platinum, reduction fully complete.
The feature of the catalyst that the present invention is synthetic is: preparation technology is simple, and after reduction, active metal is stable, and raw material sources are abundant.With commercial nickel catalyst contrast, the catalyst activity that this law makes is high, and selectively good, when iodine number is 70-90, trans-fatty acid content is lower, and after hydrogenation, the quality of grease is fine: acid value is stable and be less than 1.0 mg (KOH)/g; The slip point value of grease significantly rises, finally up to 45.08 ℃.
Accompanying drawing explanation
Fig. 1 Raney Ni and 1.79%Pt/ZrO
2the iodine number decline curve of oil with hydrogenated soybean 4h;
The C18:0 that during Fig. 2 IV ≈ 70, catalyst produces,
transc18:1 and total trans content;
Fig. 3 1.79%Pt/ZrO
2fusing point with grease after the hydrogenation of Raney Ni catalyst;
Fig. 4 1.79%Pt/ZrO
2the acid value of oil with hydrogenated soybean;
The acid value of Fig. 5 Raney Ni oil with hydrogenated soybean.
The specific embodiment
The present invention is described further with the following Examples.
The preparation condition of catalyst:
(1) carrier ZrO
2preparation: zirconyl nitrate solid is made into the aqueous solution, adds gradually ammonia spirit (1 mol/L) until produce sediment.It is centrifugal, and washing is to neutral.Solid 110 ℃ of oven dry, the Muffle furnace that is finally placed in 550 ℃ bakes 5 h;
(2) take the six hydration chloroplatinic acid solids of 160000 μ g, after dissolving with distilled water, add 3 g zirconia carriers to be made into 2%Pt/ZrO
2(vehicle weight is primary standard substance).The actual negative carrying capacity that determines platinum with ICP-AES is 1.79% Pt/ZrO
2(vehicle weight is primary standard substance);
(3) by platinum acid chloride solution and zirconia carrier continuous stirring 16 h at normal temperatures, stir and be placed on evaporated under reduced pressure in Rotary Evaporators;
(4) by synthetic solid transfer to surface plate, in 60 ℃ of vacuum drying.Then be placed in 450 ℃ of Muffle furnaces and bake 5 h;
(5) finally the catalyst after roasting is placed in to tube furnace reduction activation 6 h, reduction activation is in airtight tube furnace, to lead to nitrogen blowing with the speed temperature programming to 500 ℃ of 10 ℃/min, nitrogen replacement is become to high-purity hydrogen, reduction activation 6h in the atmosphere that is 30mL/min at hydrogen flow rate.The catalyst preparing is used nitrogen-sealed to preserve.
Catalyst effect experiment of the present invention:
Hydrogenation process condition: measure the soybean oil of 300 mL, take catalyst 150 mg(that embodiment 1 prepares and guarantee that catalyst amount is 5%, the weight of feedstock oil of take is benchmark), pour into together in hydrogenation reaction cauldron after by its good seal, start to be preheated to 170 ℃.Pass into nitrogen purge gas 2-4 minute, continuing after 3-5 minute, to keep Hydrogen Vapor Pressure with high-purity hydrogen displacement nitrogen is 3 bar, starts agitating device and makes rotating speed maintain 400 r/min, and now recording hydrogenation time is 0 h.Every 0.5 h sampling once, hydrogenation 4 h, carry out determination of iodine value to oil sample after hydrogenation altogether, each sample are carried out to vapor detection analysis simultaneously afterwards.In Fig. 2, added up the content of trans fatty acids of iodine number when 70-90,1.79%Pt/ZrO when data are presented at IV ≈ 70
2the trans C18:1 content producing is 25.48 g/100 g soybean oils, is significantly less than the trans-fatty acid content (31.42 g/100 g soybean oil) that Raney Ni produces.And the 1.79%Pt/ZrO of preparation
2stearic acid (C18:0) content that catalyst produces, also slightly lower than Raney's nickel, reaches 11.78 g/100 g soybean oils.And total transisomer that the former produces is also slightly lower than Raney nickel.The industrial selective good catalyst of seeking is to produce lower monoene isomers (antiform oleic acid) content, therefore, selects the content of antiform oleic acid as the contrast index of catalyst selectivity quality, can find out 1.79%Pt/ZrO
2the antiform oleic acid content that catalyst produces is starkly lower than Raney nickel.
What table 1 was added up is that S is compared in content and the selection that two kinds of catalyst are approximately 70 o'clock all kinds of aliphatic acid in iodine number
1, S
2.Statistics shows, 1.79%Pt/ZrO
2s is compared in the selection of catalyst
1be 1.06 higher than Raney nickel (0.87).The catalyst that zirconia-supported platinum is described can generate more monounsaturated fatty acids, and S is compared in its selection
2be 0.17, lower than Raney nickel, imply that content that C18:1 in its hydrogenation process is converted into C18:0 still less.
According to contrasting iodine number rate of descent after Fig. 1 hydrogenation, result shows that the double bond conversion rate of loaded platinum catalyst is 84.1%, and the double bond conversion rate of commercial nickel catalyst is 29.7%.The catalyst activity that can obviously find out Supported Pt Nanoparticles is much higher than common commercial Raney nickel, and the conversion ratio of its carbon-carbon double bond is 2.83 times of the latter.Therefore on the whole, the metal platinum catalyst of comparing zirconia-supported with business nickel has very high activity, lower selective generation trans-fatty acid (C18:1), and low selective generation saturated fatty acid (C18:0).
And for the variation of oil quality after each catalyst hydrogenation, after the hydrogenation of Fig. 3 result proof loaded platinum catalyst, grease fusing point rises significantly, finally up to 45.08 ℃; It is less and all lower than 1.0 mg (KOH)/g that Fig. 4 can find out that the acid value of grease after load platinum catalyst hydrogenation changes, and is applicable to grease selective hydration, and after hydrogenation, oil quality is good.After can drawing the hydrogenation of commercial nickel catalyst in conjunction with data in Fig. 3 and Fig. 5, grease fusing point approaches room temperature, and acid value fluctuation is large, is not suitable for producing hydrogenated oil and fat.
during table 1 IV ≈ 70, the aliphatic acid of each catalyst oil with hydrogenated soybean forms
| Content of fatty acid (g/100 g oil) | Soy bean oil | 1.79%Pt/ZrO 2 | Raney Ni |
| C16:0 | 13.84 | 17.63 | 22.52 |
| C18:0 | 4.55 | 11.79 | 16.18 |
| C18:1t | 0 | 25.48 | 31.42 |
| C18:1c | 28.69 | 45.12 | 36.5 |
| C18:2t | 0.86 | 6.14 | 2.02 |
| C18:2c | 59.37 | 14.49 | 13.04 |
| C18:3t | 1.44 | 0.38 | 0.63 |
| C18:3c | 6.22 | 0.48 | 1.81 |
| C20:0 | 0.5 | 0.53 | 0.77 |
| Always trans | 2.29 | 32.00 | 34.07 |
| S 1 | ? | 1.06 | 0.87 |
| S 2 | ? | 0.17 | 0.29 |
| Hydrogenation time (min) | ? | 130 | 250 |
| IV | 140 | 67.50 | 98.79 |
S wherein
1=(C18:1-C18:1
0)/(C18:2
0-C18:2); S
2=(C18:0-C18:0
0)/(C18:1-C18:1
0).
Claims (3)
1. oil hydrogenation catalyst, is characterized in that: in catalyst, metal platinum content is 1.79% of carrier zirconium dioxide weight, wherein carrier zirconium dioxide ZrO
2specific area be 26.3203 m
2g
-1, aperture is 15.52589 nm, metal platinum spread loads on carrier, granular size 1 ± 0.25 nm.
2. the preparation method of catalyst according to claim 1, is characterized in that: concrete steps are as follows:
(1) carrier ZrO
2preparation: zirconyl nitrate solid is made into the aqueous solution, adds gradually 1 mol/L ammonia spirit until produce sediment; It is centrifugal, and washing is to neutral; Solid 110 ℃ of oven dry, the Muffle furnace that is finally placed in 550 ℃ bakes 5 h;
(2) by the water dissolving at normal temperatures of six hydration chloroplatinic acids, be made into and take vehicle weight as primary standard substance 2% Pt/ZrO
2;
(3) by platinum acid chloride solution and zirconia carrier continuous stirring 16 h at normal temperatures, stir and be placed on evaporated under reduced pressure in Rotary Evaporators;
(4) by synthetic solid transfer to surface plate, in 60 ℃ of vacuum drying, be then placed in 450 ℃ of Muffle furnaces and bake 5 h;
(5) finally the catalyst after roasting is placed in to tube furnace Program and is warming up to 500 ℃ of reduction activation 6 h, the catalyst preparing is used nitrogen-sealed to preserve.
3. method as claimed in claim 2, it is characterized in that the described reduction activation of step (5) is for logical nitrogen blowing in airtight tube furnace is with the speed temperature programming to 500 ℃ of 10 ℃/min, nitrogen replacement is become to high-purity hydrogen, reduction activation 6h in the atmosphere that is 30mL/min at hydrogen flow rate.
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|---|---|---|---|
| CN201310650543.3A CN103657642A (en) | 2013-12-03 | 2013-12-03 | Grease hydrogenation catalyst |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104857993A (en) * | 2015-04-21 | 2015-08-26 | 南昌大学 | Method for improving oil and fat hydrogenation catalyst activity |
| 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 |
-
2013
- 2013-12-03 CN CN201310650543.3A patent/CN103657642A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104857993A (en) * | 2015-04-21 | 2015-08-26 | 南昌大学 | Method for improving oil and fat hydrogenation catalyst activity |
| 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 |
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Application publication date: 20140326 |