CN85103783A - The manufacturing of egg albumin-palladium complex catalyst, purposes and using method - Google Patents
The manufacturing of egg albumin-palladium complex catalyst, purposes and using method Download PDFInfo
- Publication number
- CN85103783A CN85103783A CN 85103783 CN85103783A CN85103783A CN 85103783 A CN85103783 A CN 85103783A CN 85103783 CN85103783 CN 85103783 CN 85103783 A CN85103783 A CN 85103783A CN 85103783 A CN85103783 A CN 85103783A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- palladium
- hydrogenation
- egg
- egg albumin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Landscapes
- Fats And Perfumes (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to chemical technology field.The invention a kind of egg albumin-palladium complex catalyst.Catalyzer is to be the egg albumin-palladium network joint compound of carrier with gac or egg-shell meal.
Catalyzer can carry out catalytic hydrogenation to vegetable seed wet goods vegetables oil under 110～150 ℃ of temperature condition in normal pressure or low pressure (3-4 kg/cm).Catalyzer is 4 to 100 weight ratios with the grease ratio.Catalyzer can be reused more than 20 times.Catalyzer is nontoxic, is particularly useful for vegetable seed wet goods Vegetable oil lipoprotein is carried out selective catalytic hydrogenation.
Description
The invention belongs to technical field of chemistry and chemical engineering.
Obtained since the W.Normann of Britain in 1903 since the patent of HYDROGENATION OF OILS AND FATS, HYDROGENATION OF OILS AND FATS has developed into main production technology in the oil chemistry industry.Developed later grease again and carry out selective catalytic hydrogenation under the condition that catalyzer exists, the winterized stearin that makes also becomes the important source material in the foodstuffs industry.China's vegetable seed wet goods vegetable oil resource is abundant, and wherein rapeseed oil just accounts for about 40% of edible oil total amount, makes full use of vegetable seed wet goods vegetables oil raw material development foodstuffs industry, changes China people's foodstuff texture, really a problem highly significant.
In prior art, the method of food oils hydrogenation routine is to adopt nickel-copper catalyst and skeletal nickel catalyst, because of containing higher sulfide (sulphur content is about 0.1-0.6% in the rapeseed oil) in the rapeseed oil, conventional catalyzer can only use and once will make poisoning of catalyst and lost efficacy, and the temperature requirement of catalyzed reaction is also high, generally want about 200 ℃, energy consumption is also bigger.Also more complicated of the operation of catalyst regeneration in addition.Therefore can not make the people satisfied in using.
Japanese red hole four youths (daily use chemicals 77B74(1956) in 1956) use
Albumen-palladium complex is made catalyzer to containing the compound of C=N, and the compound that contains C=C carries out hydrogenation under normal temperature, normal pressure, and its transformation efficiency is all quite high, and complex catalyst all can use repeatedly repeatedly.Day nineteen eighty-two Honda mountain great three (oiling learns 31,47(1982)) carries out homogeneous catalytic hydrogenation with ammonia carboxylic metal complex catalyst to grease now, forever that certain effect is arranged.The same year (nineteen eighty-two), China Liu Han model (catalysis journal 4,311(1982)) also with poly-quinoxaline-palladium complex and polyacrylonitrile-palladium complex respectively as catalyzer to catalytic hydrogenation under normal temperature, normal pressure such as hexene, heptene, vinyl acetate resin, the content of palladium has only 0.3-1% in its catalyzer, want much less than the palladium content 5% in the common palladium carbon catalyst, but its catalytic activity to exceed an order of magnitude than the palladium with amount.Above research all not mentioned hydrogenation catalysis and other practicality report to vegetable seed wet goods Vegetable oil lipoprotein.
The invention the egg albumin-palladium complex catalyst used of a kind of HYDROGENATION OF OILS AND FATS.It is carrier that gac is adopted in invention, albumen is adsorbed on the gac securely as the complex coordination body, carries out complex reaction with palladium chloride aqueous solution again and form charcoal-albumen-Palladous chloride, albumen can the birds albumen, as Ovum Anas domestica album albumen, egg white powder etc.; Perhaps directly and palladium chloride aqueous solution formation charcoal-albumen-palladium chloride complex with egg-shell meal.Then above-mentioned complex compound is placed on logical hydrogen activation in the ethanol: charcoal-albumen-Palladous chloride+hydrogen → charcoal-egg albumin-palladium (Pd
0)+hydrogenchloride (HCl).Because above-mentioned reaction has formed valency palladium complex catalyst in addition.The palladium amount that contains of above catalyzer is 1.2%.
Rapeseed oil, Oleum Gossypii semen, soya-bean oil, peanut oil, Rice pollard oil, corn wet goods Vegetable oil lipoprotein are when catalytic hydrogenation, catalyzer with the grease ratio is: 4 to 100 weight ratios, temperature is 110-150 ℃, under the normal pressure logical hydrogen 3-4 hour, can make qualified hydrogenated edible oil production.Egg albumin-palladium complex catalyst of the present invention can be reused more than 20 times vegetable seed wet goods vegetables oil.During the catalyzer reversible poisoning, can use processing such as ethyl acetate (or sherwood oil), the detergent aqueous solution (or aqueous sodium hydroxide solution), hydrogen peroxide-ethanolic soln respectively, catalyst activity is restored.When the permanent poisoning of catalyzer, then available calcination method burnouts gac, reclaims Palladous chloride again from residue.The rate of recovery is about 90%.
Superiority of the present invention is: at first, egg albumin-palladium complex catalyst of the present invention is active higher than conventional nickel-copper catalyst and skeletal nickel catalyst, stable performance, and favorable reproducibility, and more insensitive to air, easy handling.Secondly, this catalyzer can be applicable to the hydrogenation of vegetable seed wet goods Vegetable oil lipoprotein, reuses more than 20 times, and renovation process is easily gone, and the three wastes are less.The 3rd, this catalyzer only needs just to carry out the HYDROGENATION OF OILS AND FATS reaction smoothly under 110-150 ℃ of temperature and normal pressure or low pressure, than ordinary method save energy.The 4th, this catalyzer adopts the egg albumin-palladium complexing to form, and prepared winterized stearin is through Atomic Absorption Spectrometry, and its palladium content＜0.1ppm is nontoxic to human body, is specially adapted to the manufacturing of edible hydrogenated oil.
Specific embodiment:
The manufacturing of catalyzer:
Embodiment 1
At first get 2 grams through 5%HNO
3The aqueous solution boiled 1 hour and was washed till the gac that neutral is dried with distilled water under 140 ℃ of temperature, added in the freshly prepared Ovum Anas domestica album protein solution of 20ml2%, at room temperature stirred 8 hours, filtered, and got charcoal-Ovum Anas domestica album albumen.Then it is put into 0.33% the PdCl of 12ml
2In the aqueous solution, stirred 8 hours under the room temperature, filtration (filtration) through the no palladium ion of check, a small amount of washing gets Ovum Anas domestica album albumen-PdCl
2At last it is placed in 95% the ethanol, logical hydrogen stirred 2 hours under the room temperature, activate charcoal-Ovum Anas domestica album albumen-Pd
0Catalyzer.Filter, be stored in the ethanol.
Embodiment 2
At first get 2 kilograms of gacs through water boil 1 hour, filter, dry under 120 ℃ of temperature, join in the Ovum Anas domestica album aqueous solution of 8000ml5%, room temperature stirred 8 hours, filter charcoal-Ovum Anas domestica album albumen, then it is put into the PdCl of 6000ml0.66%
2In the aqueous solution, stirring at room 8 hours is filtered, and a small amount of washing gets charcoal-Ovum Anas domestica album albumen-PdCl
2At last it is placed in the 6000ml95% ethanol, under the room temperature, logical hydrogen stirred 2 hours, activate charcoal-Ovum Anas domestica album albumen-Pd
0Complex catalyst filters, and is stored in the ethanol.
Embodiment 3
At first get 2 grams through 5%HNO
3The aqueous solution boiled 1 hour and was washed till the gac that neutral is dried with distilled water under 140 ℃ of temperature, joined in the freshly prepared Ovum Anas domestica album protein solution of 20ml, and room temperature stirred 8 hours, filter charcoal-Ovum Anas domestica album albumen.Then charcoal-Ovum Anas domestica album albumen is put into the PdCl of 12ml0.33%
2In the aqueous solution, be heated to 80 ℃, stirred 8 hours, filter, a small amount of washing gets charcoal-Ovum Anas domestica album albumen-PdCl
2Drop it off at last in 95% the ethanol.Room temperature, logical hydrogen stirred 2 hours, activate charcoal-Ovum Anas domestica album albumen-Pd
0Complex catalyst filters, and is stored in the ethanol.
Embodiment 4
At first get 2 the gram undressed oven dry gac, be placed in the freshly prepared egg white powder aqueous solution of 20ml2%, ultrasonication 10 minutes, filter charcoal-egg white powder.Then it is placed on the pdcl of 12ml0.33%
2In the aqueous solution, ultrasonication 10 minutes gets charcoal-egg white powder-pdcl
2, place it at last in 95% ethanol, room temperature, logical hydrogen stirred 2 hours, activate charcoal-egg white powder-pd
0Complex catalyst filters, and is stored in the ethanol.
Embodiment 5
(major ingredient is 0.33% the pdcl that albumen and lime carbonate are put into 12ml at first to get 2 gram 40-60 order egg-shell meals
2In the aqueous solution, room temperature stirred 4 hours, filtered, and got egg-shell meal-pdcl
2Then it is placed in 95% ethanol, under the room temperature, logical hydrogen stirred 2 hours, filter egg-shell meal-pd
0Complex catalyst.At last, it is placed in 0.01% aqueous hydrochloric acid, stirs, the foaming pore gets egg-shell meal-pd
0Complex catalyst filters, and is washed to neutrality, is stored in the ethanol.
The regeneration of catalyzer:
Embodiment 6
If HYDROGENATION OF OILS AND FATS is used when being pure hydrogen, desirable 50 gram fouled catalysts are put into ethyl acetate and are stirred, reflux 2 hours, filter, then catalyzer is put into the boiling water that contains a small amount of detergent and soaked, stir repetitive scrubbing three times, thoroughly to eliminate grease, again with the boiling water washing, filter at last, put into H
2O
2Stirring, reflux are 2 hours in the-ethanol, filter, and with the small amount of ethanol washing, get regenerated catalyst, are stored in the ethanol.
Embodiment 7
If what use during HYDROGENATION OF OILS AND FATS is the unstripped gas of synthetic ammonia or when discharging gas, desirable 50 gram poisoned catalysts are put into ethyl acetate (or sherwood oil) and stirred, reflux 2 hours is filtered then, soaks with the boiling water that contains detergent, stirs, and eliminates grease.With the boiling water washing, this is the first step at last.Then, catalyzer is put into 0.1% hydrochloric acid or 5% aqueous acetic acid stirs, reflux to eliminate the ammonia that is adsorbed, is filtered, and catalyzer is put into H
2O
2Stirring, reflux are 2 hours in the-ethanol, filter, and with the small amount of ethanol washing, get regenerated catalyst, are stored in the ethanol.
HYDROGENATION OF OILS AND FATS
Embodiment 8
Get 2 gram egg albumin-palladium complex catalysts and put into 5.0 gram purified rapeseed oils, or in the Oleum Gossypii semen, soya-bean oil, peanut oil, Semen Maydis oil, Rice pollard oil, under 110-150 ℃ of temperature, stir, logical H-H reaction 4 hours, filtered while hot, the Off-white solid winterized stearin.The fusing point of winterized stearin is between 36-40 ℃, and iodine number is between 60-70, and catalyzer can be reused more than 20 times.When poisoning of catalyst lost efficacy, used the back of can regenerating.
Embodiment 9
Get 2 kilograms of egg albumin-palladium complex catalysts and put into 50 kilograms of purified rapeseed oils, or in the Oleum Gossypii semen, soya-bean oil, peanut oil, Semen Maydis oil, Rice pollard oil, under 110-150 ℃ of temperature, stir, feeding pressure is the gas mixture (wherein hydrogeneous～60%, nitrogen～40%) of the synthetic ammonia feedstock of 4 kg/cm, reacts 4 hours, utilize the hydrogen overbottom pressure to filter, get the Off-white solid winterized stearin.The fusing point of winterized stearin is between 36-38 ℃, and iodine number is between 60-80.Catalyzer can be reused.When poisoning of catalyst lost efficacy, used the back of can regenerating.
Claims (3)
1, a kind of hydrogenation catalyst that contains palladium is characterized in that catalyzer of the present invention is to be formed by albumen and palladium complexing.
2, a kind of it is mainly used in the hydrogenation of vegetable seed wet goods Vegetable oil lipoprotein according to the described catalyzer of claim 1, carries out selective catalytic hydrogenation and makes winterized stearin.
3, a kind of when being used for the vegetable oil and fat hydrogenation of vegetable seed wet goods according to claim 1 and 2 described catalyzer, operating pressure is normal pressure or 3-4 kg/cm, and temperature is 110～150 ℃, and the repeated use number of times of catalyzer is more than 20 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85103783A CN85103783B (en) | 1985-05-08 | 1985-05-08 | Prepn. method and use of complex catalyst of egg albumin-palladium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85103783A CN85103783B (en) | 1985-05-08 | 1985-05-08 | Prepn. method and use of complex catalyst of egg albumin-palladium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85103783A true CN85103783A (en) | 1986-03-10 |
| CN85103783B CN85103783B (en) | 1988-04-13 |
Family
ID=4793433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85103783A Expired CN85103783B (en) | 1985-05-08 | 1985-05-08 | Prepn. method and use of complex catalyst of egg albumin-palladium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85103783B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415367C (en) * | 2005-03-07 | 2008-09-03 | 南开大学 | Method for preparing nano metal palladium/supporter catalyst |
| CN100431705C (en) * | 2005-03-07 | 2008-11-12 | 南开大学 | Preparation method of Pd complex compound loading catalyst |
| CN103551108A (en) * | 2013-09-25 | 2014-02-05 | 蚌埠德美过滤技术有限公司 | Long-handle flat peach pit shell modified active carbon catalysis adsorbent and preparation method thereof |
| CN104368388A (en) * | 2014-11-04 | 2015-02-25 | 华文蔚 | Method for preparing egg white protein hydrogenation catalyst containing rhodium and ferriporphyrin |
| CN107456985A (en) * | 2017-07-25 | 2017-12-12 | 中国科学院福建物质结构研究所 | A kind of selective oxidation CO catalyst, its preparation method and application |
-
1985
- 1985-05-08 CN CN85103783A patent/CN85103783B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415367C (en) * | 2005-03-07 | 2008-09-03 | 南开大学 | Method for preparing nano metal palladium/supporter catalyst |
| CN100431705C (en) * | 2005-03-07 | 2008-11-12 | 南开大学 | Preparation method of Pd complex compound loading catalyst |
| CN103551108A (en) * | 2013-09-25 | 2014-02-05 | 蚌埠德美过滤技术有限公司 | Long-handle flat peach pit shell modified active carbon catalysis adsorbent and preparation method thereof |
| CN104368388A (en) * | 2014-11-04 | 2015-02-25 | 华文蔚 | Method for preparing egg white protein hydrogenation catalyst containing rhodium and ferriporphyrin |
| CN104368388B (en) * | 2014-11-04 | 2016-08-17 | 华文蔚 | A kind of albumen hydrogenation containing rhodium and ferriporphyrin adds the preparation method of catalyst |
| CN107456985A (en) * | 2017-07-25 | 2017-12-12 | 中国科学院福建物质结构研究所 | A kind of selective oxidation CO catalyst, its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85103783B (en) | 1988-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101982236B (en) | Hydrogenation catalyst and preparation method of 1,4-cyclohexanedimethanol | |
| CN100467372C (en) | Method of preparing biomass high specific surface micro-pore carbon material | |
| CN112899709B (en) | Copper-based compound/copper nano electrode with interface synergistic effect and preparation and application thereof | |
| CN106694009B (en) | Method for preparing low-carbon dihydric alcohol by using alloy catalyst for catalyzing carbohydrate | |
| CN111036266B (en) | Preparation method of nitrogen-doped carbon catalyst and application of nitrogen-doped carbon catalyst in biological oil hydrogenation | |
| CN103272619A (en) | Anion modified mercury-free catalyst for ethyne hydrochlorination reaction, and preparation method thereof | |
| CN105126898A (en) | Preparation of hydrodeoxygenation isomerization catalyst and application thereof in preparation of diesel oil from illegal cooking oil | |
| CN85103783A (en) | The manufacturing of egg albumin-palladium complex catalyst, purposes and using method | |
| CN105126840A (en) | Efficiently supported palladium catalyst for hydrogenation process of H2O2 production with anthraquinone method and preparation method of efficiently supported palladium catalyst | |
| CN102806095B (en) | Multi-component non-mercury accelerant for preparing vinyl chloride through acetylene hydrochlorination and application method of multi-component non-mercury accelerant | |
| CN105314648A (en) | CHA-type silicon-aluminum molecular sieves, and preparation methods and applications thereof | |
| CN103191764A (en) | Mercury-free catalyst for synthesizing vinyl chloride through acetylene hydrochlorination and preparation method thereof | |
| CN115672316A (en) | Biomass framework carbon-metal composite micro-nano structure catalytic material, preparation method and application | |
| CN101618325B (en) | Method for preparing zirconium-yttrium composite pillared montmorillonite supported cobalt catalyst | |
| CN108786802A (en) | A kind of room temperature purify the air of a room pollutant method for preparing catalyst and its application | |
| CN1239679A (en) | Catalyst for dehydrogenation of saturated hydrocarbon and its preparation | |
| CN114210340A (en) | High-activity gas-phase synthesis dimethyl carbonate catalyst and preparation method and application thereof | |
| CN1053017A (en) | Catalyst of carbon monoxide oxidation (palladium-nickel/tin ash) and preparation method thereof | |
| CN1070128A (en) | A kind of palladium/manganese oxide deoxidizing agent | |
| CN100457865C (en) | Acetylene selected hydrogenation catalyst and its preparation method | |
| CN114029052A (en) | Regeneration method of mercury-free noble metal catalyst for acetylene hydrochlorination | |
| CN103990497B (en) | A kind of preparation method of wool loaded with nano Pd-Co catalyst and application | |
| CN1247447C (en) | Catalyzer for preparing synthetic gas from natural gas partial oxidation and its preparation method | |
| CN113385179A (en) | Nickel-loaded activated carbon with large specific surface area | |
| CN111744482A (en) | High specific surface nickel loaded active carbon material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |