CN102329693B - Method for preparing high-quality fine lacquer wax product - Google Patents
Method for preparing high-quality fine lacquer wax product Download PDFInfo
- Publication number
- CN102329693B CN102329693B CN201110230852.6A CN201110230852A CN102329693B CN 102329693 B CN102329693 B CN 102329693B CN 201110230852 A CN201110230852 A CN 201110230852A CN 102329693 B CN102329693 B CN 102329693B
- Authority
- CN
- China
- Prior art keywords
- lacquer
- tree fat
- lacquer tree
- wax
- hunter
- 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.)
- Expired - Fee Related
Links
- 239000004922 lacquer Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 8
- 244000044283 Toxicodendron succedaneum Species 0.000 claims description 107
- 239000003925 fat Substances 0.000 claims description 103
- 238000005984 hydrogenation reaction Methods 0.000 claims description 58
- 239000003973 paint Substances 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 34
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- 239000000284 extract Substances 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000003921 oil Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 11
- 229910052740 iodine Inorganic materials 0.000 claims description 11
- 239000011630 iodine Substances 0.000 claims description 11
- 238000002137 ultrasound extraction Methods 0.000 claims description 10
- 229960000892 attapulgite Drugs 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052625 palygorskite Inorganic materials 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000003801 milling Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 17
- 150000004670 unsaturated fatty acids Chemical class 0.000 abstract description 15
- 235000021122 unsaturated fatty acids Nutrition 0.000 abstract description 15
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 5
- 239000000194 fatty acid Substances 0.000 abstract description 5
- 229930195729 fatty acid Natural products 0.000 abstract description 5
- 238000004817 gas chromatography Methods 0.000 abstract description 5
- 150000004665 fatty acids Chemical class 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 229940045860 white wax Drugs 0.000 abstract 1
- 239000001993 wax Substances 0.000 description 32
- 239000003760 tallow Substances 0.000 description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 10
- 239000005642 Oleic acid Substances 0.000 description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 10
- 238000012545 processing Methods 0.000 description 9
- 238000007670 refining Methods 0.000 description 9
- 150000002632 lipids Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000012174 chinese wax Substances 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- -1 tetracol phenixin Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000000556 factor analysis Methods 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229960004232 linoleic acid Drugs 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- 241000208223 Anacardiaceae Species 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 241000159241 Toxicodendron Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 1
- 239000012182 japan wax Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000003248 secreting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Fats And Perfumes (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing high-quality fine lacquer wax product, which comprises the following steps of: firstly, microwave drying lacquer seeds, separating skin and cores, and lixiviating the skin and flesh part of the lacquer seeds by using a non-polar solvent to obtain rough lacquer wax; heating and uniformly mixing the lacquer wax and a certain proportion of Pd/C catalyst in a high-temperature high-pressure reactor, charging hydrogen gas and maintaining a certain hydrogen gas pressure for reaction; after the reaction is completed, and filtering and discoloring the product while hot to obtain highly saturated lacquer wax; and detecting the variation of fatty acid content in the lacquer wax, by using gas chromatography. The method is simple and convenient, and the problems of low lacquer wax melting point, easy rancidity and the like caused by high content of unsaturated fatty acid in rough lacquer wax can be effectively solved. The obtained hydrogenated fine lacquer wax product has similar physical and chemical properties to Star Cherry-A white wax processed by Japan Araki Wax Manufacturing Company and can be widely applied to the field of daily chemicals.
Description
Technical field
The present invention relates to a kind of vegetable wax chemical conversion technical field, specifically, is a kind ofly to using palladium carbon as catalyzer, and lacquer tree fat is carried out to chemical modification, prepares the method for the high-quality fine lacquer wax product of high saturation.
Background technology
Lacquer tree mainly refers to that Anacardiaceae, paint belong to a class plant of Toxicodendron, be one of traditional economic forest of China, its cultivation history is long, and variety source is abundant, because secreting a kind of lacquer (being raw lacquer), there is unique Optimality and be called as state paint or lacquer, enjoy great prestige both at home and abroad.The fruit of lacquer tree claims again to paint seed, is flat tiltedly spherical, and annual 9～October of autumn is ripe.Pericarp divides 3 layers, and exocarp is membranous; Mesocarp is wax layer, can extract lacquer tree fat, is light yellow or greyish-green; Kernel is seed, can squeeze urushoil.In existing lacquer tree colony, there is more than 30 kind strain more than 100,000,000 to set seeds, produce approximately more than 200 ten thousand tons of paint seed amounts per year, rank first in the world.
Rough lacquer tree fat outward appearance is pale yellow, greyish white or greyish-green solid, and refining Japan wax is shallow milk look wax after decolouring is processed.Refining lacquer tree fat has gluing sense, not hard, but flexible has tallow smell, places meeting frosting and blackening, easily break, and breach mattness.Dissolve in hot ethanol, dithiocarbonic anhydride, chloroform, ether, benzene, sherwood oil, tetracol phenixin, toluene, trichloroethane and turpentine wet goods.Relative density (20 ℃/20 ℃) 0.975～0.984d. refractive indexs (60 ℃) 1.450～1.456, insolubles impurity is less than 0.03%, weight loss on heating is less than 0.03%, 50～56 ℃ of molten points, iodine number 4～25, saponification value 200～240, acid number 6～20, unsaponifiables quality mark is 2%～5%.Its chemical composition is by 90%～95% Witepsol W-S 55,3%～15% free fatty acids, and 1%～2% free alkyl alcohol forms, wherein tie platform lipid acid by 70%～75% palmitinic acid, 3%～5% stearic acid, 15%～35% oleic acid, 2%～5% binary of fatty acids forms.
Lacquer tree fat is a kind of important industrial chemicals, directly separation and purification palmitinic acid, stearic acid, oleic acid and linolic acid and salt thereof.From lacquer tree fat, can also refine the high fatty alcohols such as triacontanol price quote, it is the significant surfaces promoting agent of the industries such as soapmaking, washing, lubricated, plasticising, makeup, not only import plam oil can be replaced, for country saves a large amount of foreign exchanges, and the domestic and international market of haze tallow can be expanded.Especially the fatty acid cane sugar ester of being processed by haze tallow, isopropyl fatty acid ester (Wickenol 111 is main) is applied very extensive in the world, is used in particular for the aspects such as superior cosmetics, emulsifying agent.
The defect of lacquer tree fat is that softening temperature is low, and acid number is high, the physical and chemical performance of the lacquer tree fat that the Star Cherry-A board Chinese wax of Japan waste wooden wax company processing obviously improves.Yet the processing and utilization of China's paint seed is also nowhere near.Be that traditional concept does not change on the one hand, follow with raw lacquer and be processed as master always; Be because paint seed complete processing is backward and haze tallow deep processed product cost is high, small scale on the other hand, thereby limited the processing and utilization of haze tallow.Especially the analysis of the refining wax of Japanese Star Cherry-A is being found to the content of its unsaturated fatty acids (being mainly oleic acid) only has 1.90%～2.90%, and in Chinese haze tallow the content of unsaturated fatty acids up to 15%～25%.The unsaturated fatty acids of high-content not only makes the fusing point of haze tallow lower than the refining haze tallow of Japan, and easy oxidative rancidity, has reduced its quality.
In order to improve performance and the quality of Chinese lacquer tree fat, expand its purposes, the present invention adopts the method for microwave treatment, shortening, decolouring, take palladium carbon as catalyzer, by undersaturated lipid acid in lacquer tree fat, be mainly oleic acid and linolic acid, be converted into saturated stearic acid, make the refining haze tallow of its chemical composition and Japan more approaching, thereby promote its meticulous utilization.
Summary of the invention
The object of the present invention is to provide a kind of method of high-quality fine lacquer wax product, to solve in lacquer tree fat, the high fusing point causing of unsaturated fatty acid content is low, the easy problem such as become sour, another object is to make the chemical composition of lacquer tree fat more approaching with Japanese refining haze tallow, to promote the outlet of lacquer tree fat and to become more meticulous utilization etc.
For realizing above object, the present invention adopts the method for microwave treatment, shortening, decolouring, take palladium carbon as catalyzer, in high-temperature high-pressure reaction kettle, lacquer tree fat is carried out to hydrogenation reaction, and unsaturated fatty acids is wherein converted into saturated lipid acid, and concrete steps are:
The first step: the pre-treatment of raw material
Before being used, paint seed adopts microwave drying, microwave power 100-800W, microwave exposure 30-300s, with blade type crusher or runner milling, pulverize paint seed, the sieve more than 20 orders, removes upper strata seed nuclei, the pulp fraction of sifting out paint seed, water ratio is lower than 6%, and fat content is higher than 45%.
Second step: the preparation of rough lacquer tree fat
The paint seed pulp fraction that adopts non-polar solvent lixiviate to dry, the volume ratio of paint seed pulp fraction quality and extraction solvent is 1: 6-30 (g/ml), temperature 0-90 ℃, extract 10-360min, extract 1-3 time, after filtering, merge vat liquor, vacuum concentration under 30-60 ℃ of condition, enriched material is cooled to room temperature, obtains the rough lacquer tree fat of pale green grey;
The 3rd step: the hydrogenation reaction of lacquer tree fat
Rough lacquer tree fat is inserted in high-temperature high-pressure reaction kettle, add palladium-carbon catalyst, catalyst levels is the 0.1%-1.0% of lacquer tree fat quality.Reactor is warmed up to 70 ℃ of lacquer tree fats and melts completely as liquid state, stirs catalyzer is fully mixed, and stirring velocity is 60-300rpm, is filled with hydrogen, and controls hydrogen pressure and maintain 0.1-1MPa, temperature of reaction 80-160 ℃, reaction times 1-8h;
The 4th step: palladium carbon reclaims
After hydrogenation reaction is complete, filtered while hot, filter residue washs 2-3 time at 50-100 ℃ of 1M sodium hydroxide solution, then washes 2-3 time with deionized water, reclaims palladium carbon, recycle 4-10 time;
The 5th step, the decolouring of hydrogenation lacquer tree fat
Hydrogenation lacquer tree fat filtrate is maintained the temperature to 50-80 ℃, and gac and attapulgite are 1 in mass ratio: 1-10 is as discoloring agent, and discoloring agent and hydrogenation lacquer tree fat crude product mass ratio are 1: 20-200, stirs decolouring 10-80min.Plate Filtration, filtrate is put into pallet, naturally cooling, the fine lacquer wax product that preparation whiteness is greater than 90, its acid number and iodine number are less than 10.
The 6th step: fine lacquer wax product whiteness performance measurement
The mensuration of fine lacquer wax product whiteness adopts WSC-S colour examining colour-difference-metre, is adjusted into Hunter system, and preheating 30min, measures its L
*, a
*, b
*, E value, utilize Hunter (hunter) completely whiteness formulas calculate its whiteness (W).
W＝100-[(100-L
*)
2+a
*2+b
*2]
1/2
Hunter (Hunter) whiteness of W-fine lacquer wax product sample; L
*-Hunter (Hunter) lightness index; a
*, b
*-Hunter (Hunter) chromaticity index.
The 7th step: fine lacquer wax product chemical constituents determination
The fine lacquer wax product that takes a morsel carries out esterification, adopts the variation of its lipid acid relative content of GC-MS chromatography determination.GC condition: carrier gas is the helium of purity 99.99%, fused-silica capillary column
5MS 15m * 0.25mm, 250 ℃ of injection port temperature, 110 ℃ of post initial temperature, insulation 10min, rises to 220 ℃ with 10 ℃/min temperature rise rate, insulation 18min.Before post, press 90kPa, splitting ratio 50: 1, sample size 1 μ l.MS condition: 280 ℃ of interface temperature, ion source is selected EI source, electron energy 70eV, 230 ℃ of ion source temperatures, photomultiplier transit tube voltage 2200V, sweep limit 29.0-450.0u, mass spectral database NIST.
The refining wax physical and chemical performance of Japan Star Cherry-A is: molten some 50-54 ℃, acid number 15-20, iodine number 5-18, saponification value 205-225, the relative content of chemical constitution palmitinic acid is 76.40%, stearic relative content is 17.60%, and the relative content of oleic acid is 2.90%, and the content of Chinese lacquer tree fat unsaturated fatty acids is up to 10%-20%.The unsaturated fatty acids of high-content not only makes the fusing point of haze tallow lower than the refining haze tallow of Japan, and easy oxidative rancidity, has reduced its quality.As table 1.
The Chinese lacquer tree fat of table 1 and the contrast of Japanese haze tallow chemical constitution
Chinese lacquer cerinic acid value and iodine number are higher, high mainly due to water content in raw material, before processing, go mouldy and cause and become sour, in order to reduce the acid number in Chinese lacquer tree fat, this patent adopts microwave drying sterilization to remove enzyme first, microwave power 100-800W, preferred 200-400W, microwave exposure 30-300s, preferred 60-200s, microwave exposure not only can be dried, remove moisture content, make the pulp fraction water ratio that paints seed lower than 6%, and microwave exposure has shell-broken effect, with blade type crusher or runner milling, pulverize paint seed, Pi Ren is more easily separated, pulp fraction is easily broken, sieve more than 20 orders, remove upper strata seed nuclei, sift out fat content higher than 45% pulp skin powder.
This patent carries out the pulp skin powder of Microwave Pretreatment to paint seed raw material, adopt non-polar solvent lixiviate, non-polar solvent is sherwood oil (60～120 ℃), No. 6 solvent oils, a kind of in ether, normal hexane, pentane etc., preferably sherwood oil (60～120 ℃), No. 6 solvent oils and normal hexane.Lixiviate mode can adopt in Soxhlet extraction, thermal backflow extraction and ultrasonic extraction a kind of, Soxhlet is extracted temperature 60-70 ℃, extract 180min-360min, temperature 60-90 ℃ is extracted in thermal backflow, extract 30min-180min, ultrasonic extraction power 50-400W, extracts temperature 0-50 ℃, extracts 10min-30min; Preferred ultrasonic extraction.
Catalyzer is a kind of gordian technique and the material in oil hydrogenation industry, directly affects the quality and performance of product.Conventionally the commercial catalysts adopting is nickeliferous or the catalyzer of copper, yet the existence of trace copper makes grease accelerate to ruin, and nickel has carcinogenesis to human body, so noble metal catalyst, particularly palladium, platinum catalyst are invested sight by increasing country.These catalyzer not only have high catalytic activity, selectivity, and can reduce the residual of the content of trans acids and catalyzer.This patent is selected palladium-carbon catalyst, and the charge capacity of C catalyst palladium is 2%～10%, and preferably 3%～7%.
In order to reduce iodine number, improve lacquer tree fat saturation ratio and fusing point, this patent adopts hydrogenation reaction.In high-temperature high-pressure reaction kettle, add palladium-carbon catalyst, catalyst levels is the 0.1%-1.0% of lacquer tree fat quality.Reactor is warmed up to 70 ℃ of lacquer tree fats and melts completely as liquid state, stirs catalyzer is fully mixed, and stirring velocity is 60-300rpm, is filled with hydrogen, and controls hydrogen pressure and maintain 0.1-1MPa, temperature of reaction 80-160 ℃, reaction times 1-8h.
It is catalyzer that this patent be take palladium carbon (5.0%), at hydrogen pressure 0.5MPa, under the condition that temperature is 100 ℃, react 2h, result as shown in Figure 1, increase with palladium carbon consumption, the transformation efficiency of unsaturated fatty acids also increases thereupon, and the relative content of saturated fatty acid increases, and the relative content of unsaturated fatty acids reduces.Consider that palladium carbon is expensive, increasing its usage quantity can raise the cost, and therefore, the preferred palladium carbon of this patent usage quantity is 0.2% more applicable.
It is catalyzer that this patent be take Pd/C (5%), and consumption is 0.15%, at 100 ℃, reacts respectively 2h, 4h and 6h under the condition of 0.5MPa.As shown in Figure 2, with the prolongation in reaction times, the transformation efficiency of unsaturated fatty acids raises result, but after 2h to the longer time, it is not clearly that stearic relative content changes.In addition, the long more multipotency that not only consumes of reaction times, raises the cost, and with the decline of hydrogen pressure, also easily causes the decline of lacquer tree fat quality, as acid value rising, oxidative stability reduction etc.React the lacquer tree fat of 6 hours with regard to obviously the lacquer tree fat color than 2-4 hour is dark.Therefore, the suitable time of this patent lacquer tree fat hydrogenation is excellent selects at 2-4h.
This patent adds Pd/C catalyzer (0.15%), under the condition of hydrogen pressure 0.5MPa, reacts 2h, and temperature is respectively 80,100 and 120 ℃, and result as shown in Figure 3.By accompanying drawing 3, can be found out, temperature of reaction has a certain impact to lacquer tree fat hydrogenation tool, and with the rising of temperature, transformation efficiency also increases, and too high temperature of reaction not only will consume the energy, also easily makes the metal nucleus of catalyzer be heated and grow up and reduce the activity of catalyzer.Therefore, the preferred 100 ℃ of left and right of this patent.
This patent adds Pd/C catalyzer (0.15%), at 100 ℃, reacts 2h, and hydrogen pressure is respectively 0.3,0.5 and 0.7MPa.Shown in accompanying drawing 4, hydrogen pressure rises to 0.7MPa by 0.3MPa, and some changes the relative content of stearic acid and unsaturated fatty acids, especially between 0.3MPa to 0.5MPa.And too high pressure not only can cause the waste of resource, also dangerous in Specific construction.Therefore, the preferred 0.5MPa of the suitable pressure of this patent lacquer tree fat hydrogenation left and right.
This patent passes through single factor analysis, the suitable condition of lacquer tree fat hydrogenation is: catalyzer (5% palladium carbon) consumption 0.1%～0.5%, preferably 0.2%～0.3%, reaction times 2～8h, preferred 2～4h, 80～120 ℃ of temperature ranges, preferably 90～100 ℃, hydrogen pressure maintains 0.3～1MPa, preferably 0.4～0.7MPa.
Palladium catalyst is more expensive, in order to reduce production costs, this patent, in the renovation process of palladium catalyst alkali liquid washing, mainly adopts overheated sodium hydroxide solution washing to be attached to the organism such as glycerin fatty acid ester on palladium catalyst surface, thereby makes palladium crystal grain have activity.After hydrogenation reaction is complete, filtered while hot, filter residue washs 2-3 time at 50-100 ℃ of 1M sodium hydroxide solution, then washes 2-3 time with deionized water, reclaims palladium-carbon catalyst, reusable edible 4-10 time.
The discoloring agents such as charcoal and molecular sieve decolouring for this patent screening plain particles charcoal, decolouring phosphoric acid charcoal for sugar, monosodium glutamate decolouring, atlapulgite, attapulgite, mixing discoloring agent, adopt orthogonal test L
9(3
4) determine and best decolorization condition hydrogenation lacquer tree fat filtrate is maintained the temperature to 50-80 ℃, gac and attapulgite are 1 in mass ratio: 1-10 is as discoloring agent, preferably 1: 1-5; Discoloring agent and hydrogenation lacquer tree fat crude product mass ratio are 1: 20-200, and preferably 1: 150-200, stirs decolouring 10-80min, preferably 10-30min.Plate Filtration, filtrate is put into pallet, naturally cooling, the fine lacquer wax product that preparation whiteness is greater than 90, obtains best decolorizing effect.As table 2
The decolouring impact of the different discoloring agents of table 2 on hydrogenation lacquer tree fat
This patent adopts gas chromatography analysis method, lacquer tree fat before and after hydrogenation is carried out to chemical composition analysis, analytical results is as accompanying drawing 5, accompanying drawing 6 and table 3, after hydrogenation, stearic relative content obviously raises, reach 15.85%, and the relative content of oleic acid obviously reduces, the relative content of palmitinic acid changes and is not obvious.As shown in Figure 7, in the Star Cherry-A board Chinese wax of Japan waste wooden wax company processing, the relative content of palmitinic acid is 76.40%, stearic relative content is 17.60%, the relative content of oleic acid is 2.90%, and linoleic content is 0, and the lacquer tree fat after this and hydrogenation is more approaching, therefore, this patent approaches with Japanese refining Chinese wax by the physical and chemical performance of the fine lacquer wax product of hydrogenation and decolouring preparation.
Lacquer tree fat main fatty acid ratio analysis before and after table 3 hydrogenation
Note: a-b is respectively the lacquer tree fat before and after hydrogenation, c be the Star Cherry-A board Chinese wax of Japanese waste wooden wax company.
Beneficial effect of the present invention shows as:
1. adopt first microwave drying sterilization to remove enzyme pre-treatment paint seed, not only can be dried, remove moisture content, make the pulp fraction water ratio that paints seed lower than 6%, and microwave exposure has shell-broken effect, with blade type crusher or runner milling, pulverize paint seed, Pi Ren is more easily separated, and pulp fraction is easily broken, sieve more than 20 orders, remove upper strata seed nuclei, sift out fat content higher than 45% pulp skin powder, effectively prevent that lacquer tree fat from going mouldy and causing that acid number raises.
2. adopt first the pretreated paint seed of ultrasonic extraction microwave drying, the extraction yield of lacquer tree fat is greater than 98%, and more traditional thermal backflow and Soxhlet are extracted, and temperature is low, and the time is short, and efficiency is high.
3. adopt first palladium-carbon catalyst to carry out hydrogenation to lacquer tree fat, prepare the lacquer tree fat of high saturation, its iodine number, lower than 10, obviously improves the hardness of lacquer tree fat.
4. adopt gac and attapulgite clay compounded discoloring agent, the fine lacquer wax product that preparation whiteness is greater than 90, obtains best decolorizing effect, and acid number is less than 7, has obviously reduced the acid number of product, efficiently solves the problem that lacquer tree fat fusing point is low, easily become sour.
Accompanying drawing explanation:
Accompanying drawing 1 is the impact of palladium carbon consumption on lacquer tree fat hydrogenation process
Accompanying drawing 2 is the impact of time on lacquer tree fat hydrogenation process
The impact of accompanying drawing 3 temperature on lacquer tree fat hydrogenation process
Accompanying drawing 4 is the impact of pressure on lacquer tree fat hydrogenation process
The gas chromatogram that accompanying drawing 5 is rough lacquer tree fat
Accompanying drawing 6 is lacquer tree fat gas chromatogram after hydrogenation
Accompanying drawing 7 is the total ion current figure of the Star Cherry-A board Chinese wax of Japan waste wooden wax company.
Embodiment
Following examples are more of the present invention giving an example, and should not be seen as limitation of the invention.
The preparation of embodiment 1 high-quality fine lacquer wax product
The first step: the pre-treatment of raw material
Before being used, paint seed adopts microwave drying, microwave power 100-800W, preferred 200-400W, microwave exposure 30-300s, preferably 60-200s; With blade type crusher or runner milling, pulverize paint seed, the sieve more than 20 orders, removes upper strata seed nuclei, sifts out the pulp fraction of paint seed, and wherein water ratio is lower than 6%, and fat content is higher than 45%;
Second step: the preparation of rough lacquer tree fat
The paint seed powder that adopts non-polar solvent lixiviate to dry, non-polar solvent is sherwood oil (60～120 ℃), No. 6 solvent oils, a kind of in ether, normal hexane, pentane etc., preferably sherwood oil (60～120 ℃), No. 6 solvent oils and normal hexane.The volume ratio of paint seed pulp fraction quality and extraction solvent is 1: 6-30 (g/ml), lixiviate mode adopts in Soxhlet extraction, thermal backflow extraction and ultrasonic extraction a kind of, as Soxhlet is extracted temperature 60-70 ℃, extract 180min-360min, temperature 60-90 ℃ is extracted in thermal backflow, extracts 30min-180min, ultrasonic extraction power 50-400W, extract temperature 0-50 ℃, extract 10min-30min; Preferred ultrasonic extraction.Extract 1-3 time, after filtering, merge vat liquor, vacuum concentration under 30-60 ℃ of condition, enriched material is cooled to room temperature, obtains the rough lacquer tree fat of pale green grey, and extraction yield is greater than 95%;
The 3rd step: the hydrogenation reaction of lacquer tree fat
Rough lacquer tree fat is inserted in high-temperature high-pressure reaction kettle, add palladium-carbon catalyst, catalyst levels is the 0.1%-1.0% of lacquer tree fat quality.Reactor is warmed up to 70 ℃ of lacquer tree fats and melts completely as liquid state, stirs catalyzer is fully mixed, and stirring velocity is 60-300rpm, is filled with hydrogen, and controls hydrogen pressure and maintain 0.1-1MPa, temperature of reaction 80-160 ℃, reaction times 1-8h; The charge capacity of palladium-carbon catalyst palladium is 2%～10%, preferably 3%～7%;
This patent passes through single factor analysis, the top condition of lacquer tree fat hydrogenation is: catalyzer (5% palladium carbon) consumption 0.1%～0.5%, preferably 0.2%～0.3%, reaction times 2～8h, preferred 2～4h, 80～120 ℃ of temperature ranges, preferably 90～100 ℃, hydrogen pressure maintains 0.3～1MPa, preferably 0.4～0.7MPa;
The 4th step: palladium carbon reclaims
After hydrogenation reaction is complete, filtered while hot, filter residue is at 50-100 ℃, and preferably 80-90 ℃, with 1M sodium hydroxide solution washing 2-3 time, then washes 2-3 time with deionized water, reclaims palladium carbon, recycle 4-10 time, preferably 4-6 time;
The 5th step, the decolouring of hydrogenation lacquer tree fat
Adopt orthogonal test L
9(3
4) determine and best decolorization condition hydrogenation lacquer tree fat filtrate is maintained the temperature to 50-80 ℃, gac and attapulgite are 1 in mass ratio: 1-10 is as discoloring agent, preferably 1: 1-5; Discoloring agent and hydrogenation lacquer tree fat crude product mass ratio are 1: 20-200, and preferably 1: 150-200, stirs decolouring 10-80min, preferably 10-30min.Plate Filtration, filtrate is put into pallet, naturally cooling, the fine lacquer wax product that preparation whiteness is greater than 90, acid number and iodine number are less than 10;
The 6th step: fine lacquer wax product whiteness performance measurement
The mensuration of fine lacquer wax product whiteness adopts WSC-S colour examining colour-difference-metre, is adjusted into Hunter system, and preheating 30min, measures its L
*, a
*, b
*, E value, utilize Hunter (hunter) completely whiteness formulas calculate its whiteness (W).
W＝100-[(100-L
*)
2+a
*2+b
*2]
1/2
Hunter (Hunter) whiteness of W-fine lacquer wax product sample; L
*-Hunter (Hunter) lightness index; a
*, b
*-Hunter (Hunter) chromaticity index;
The 7th step: fine lacquer wax product chemical constituents determination
The fine lacquer wax product that takes a morsel carries out esterification, adopts the variation of its lipid acid relative content of GC-MS chromatography determination.GC condition: carrier gas is the helium of purity 99.99%, fused-silica capillary column
-5 MS 15m * 0.25mm, 250 ℃ of injection port temperature, 110 ℃ of post initial temperature, insulation 10min, rises to 220 ℃ with 10 ℃/min temperature rise rate, insulation 18min.Before post, press 90kPa, splitting ratio 50: 1, sample size 1 μ L.MS condition: 280 ℃ of interface temperature, ion source is selected EI source, electron energy 70eV, 230 ℃ of ion source temperatures, photomultiplier transit tube voltage 200V, sweep limit 29.0-450.0u, mass spectral database NIST.
The first step: the preparation of rough lacquer tree fat
Paint seed 500g, puts into 400W microwave device microwave exposure 180s, cooling, then microwave exposure 30s, cooling, with blade type crusher or runner milling, pulverize paint seed, the sieve more than 20 orders, removes upper strata seed nuclei, the fruit powder that sifts out paint seed, wherein water ratio is lower than 6%, and fat content is higher than 45%.
Take sherwood oil as solvent, and the volume ratio of paint seed fruit powder and extraction solvent is 1: 20g/ml, and 80 ℃ of temperature, extract 2h, extract 2 times, after filtering, merge vat liquor, vacuum concentration under 60 ℃ of conditions, enriched material is cooled to room temperature, obtains rough lacquer tree fat, yield 96%;
Second step: the hydrogenation process of lacquer tree fat
Rough lacquer tree fat is inserted in high-temperature high-pressure reaction kettle, and to add 0.15% charge capacity be 0.5% palladium-carbon catalyst, stirring heats up fully mixes it, and stirring velocity is 200rpm, 100 ℃ of temperature ranges; Be filled with hydrogen, and control hydrogen pressure and maintain 0.5MPa, reaction 6h;
The 3rd step: the processing after lacquer tree fat hydrogenation
After hydrogenation reaction is complete, filtered while hot is washed 3 times with 1M sodium hydroxide solution, then is washed 3 times with deionized water at 80 ℃, reclaims palladium carbon.Hydrogenation lacquer tree fat filtrate is maintained the temperature to 80 ℃, gac and attapulgite be in mass ratio 1: 2 as discoloring agent, discoloring agent and hydrogenation lacquer tree fat crude product mass ratio are 1: 200, stir decolouring 30min.Plate Filtration, filtrate is put into pallet, naturally cooling, the fine lacquer wax product that preparation whiteness is greater than 90, acid number and iodine number are less than 10;
The 4th step: the mensuration of lacquer tree fat chemical composition
The lacquer tree fat taking a morsel after hydrogenation and decolouring carries out esterification, adopts the variation of its lipid acid relative content of gas chromatography determination.Analytical results shows, in fine lacquer wax product, unsaturated fatty acids is mainly that oleic acid and linoleic relative content have dropped to 4% by 14%, and stearic content is raised to 17% by 7%.
The first step: the preparation of rough lacquer tree fat
Before being used, paint seed uses microwave drying, with blade type crusher or runner milling, pulverize paint seed, cross 40 object sieves, dust is the pulp fraction of paint seed, and the pulp fraction of getting paint seed, take normal hexane as solvent, the volume ratio of paint seed pulp fraction quality and extraction solvent is 1: 15g/ml, ultrasonic extraction power 400W, extracts 30 ℃ of temperature, extracts 20min; Extract 2 times, after filtering, merge vat liquor, vacuum concentration under 60 ℃ of conditions, enriched material is cooled to room temperature, obtains rough lacquer tree fat, extraction yield 98%;
Second step: the hydrogenation process of lacquer tree fat
Rough lacquer tree fat is inserted in high-temperature high-pressure reaction kettle, and to add 0.3% charge capacity be 0.5% palladium-carbon catalyst, stirring heats up fully mixes it, and stirring velocity is 200rpm, 120 ℃ of temperature ranges; Be filled with hydrogen, and control hydrogen pressure and maintain 0.5MPa, reaction 1.5h;
The 3rd step: the processing after lacquer tree fat hydrogenation
After hydrogenation reaction is complete, filtered while hot is washed 2 times with 1M sodium hydroxide solution, then is washed 3 times with deionized water at 70 ℃, reclaims palladium carbon.Hydrogenation lacquer tree fat filtrate is maintained the temperature to 70 ℃, gac and attapulgite be in mass ratio 1: 1 as discoloring agent, discoloring agent and hydrogenation lacquer tree fat crude product mass ratio are 1: 150, stir decolouring 30min.Plate Filtration, filtrate is put into pallet, naturally cooling, the fine lacquer wax product that preparation whiteness is greater than 90, acid number and iodine number are less than 10;
The 4th step: the mensuration of lacquer tree fat chemical composition
The lacquer tree fat taking a morsel after hydrogenation and decolouring carries out esterification, adopts the variation of its lipid acid relative content of gas chromatography determination.Analytical results shows, in fine lacquer wax product, unsaturated fatty acids is mainly that oleic acid and linoleic relative content have dropped to 6.5% by 14%, and stearic content is raised to 14.7% by 7%.
The first step: the preparation of rough lacquer tree fat
Before paint seed is used, with microwave drying, with blade type crusher or runner milling, pulverize paint seed, cross 40 object sieves, dust is the pulp fraction of paint seed, the pulp fraction of getting paint seed, No. 6 solvent oils of take are solvent, the volume ratio of paint seed pulp fraction quality and extraction solvent is 1: 20g/ml, Soxhlet is extracted 65 ℃ of temperature, extract 5 hours, vat liquor is vacuum concentration under 60 ℃ of conditions, and enriched material is cooled to room temperature, obtain rough lacquer tree fat, extraction yield 97%;
Second step: the hydrogenation process of lacquer tree fat
Rough lacquer tree fat is inserted in high-temperature high-pressure reaction kettle, and to add 0.5% charge capacity be 0.5% palladium-carbon catalyst, stirring heats up fully mixes it, and stirring velocity is 200rpm, 100 ℃ of temperature ranges; Be filled with hydrogen, and control hydrogen pressure and maintain 0.7MPa, reaction 2h;
The 3rd step: the processing after lacquer tree fat hydrogenation
After hydrogenation reaction is complete, filtered while hot is washed 2 times with 1M sodium hydroxide solution, then is washed 2 times with deionized water at 65 ℃, reclaims palladium carbon.Hydrogenation lacquer tree fat filtrate is maintained the temperature to 65 ℃, gac and attapulgite be in mass ratio 1: 5 as discoloring agent, discoloring agent and hydrogenation lacquer tree fat crude product mass ratio are 1: 180, stir decolouring 30min.Plate Filtration, filtrate is put into pallet, naturally cooling, the fine lacquer wax product that preparation whiteness is greater than 90, acid number and iodine number are less than 10;
The 4th step: the mensuration of lacquer tree fat chemical composition
The lacquer tree fat taking a morsel after hydrogenation and decolouring carries out esterification, adopts the variation of its lipid acid relative content of gas chromatography determination.Analytical results shows, in hydrogenation lacquer tree fat essence, unsaturated fatty acids is mainly that oleic acid and linoleic relative content have dropped to 5% by 14%, and stearic content is raised to 16% by 7%.
Claims (3)
1. a preparation method for high-quality fine lacquer wax product, is characterized in that being comprised of following steps:
The first step: the pre-treatment of raw material
Before being used, paint seed adopts microwave drying, microwave power 100～800W, microwave exposure 30～300s, with blade type crusher or runner milling, pulverize paint seed, the sieve more than 20 orders, removes upper strata seed nuclei, the pulp fraction of sifting out paint seed, water ratio is lower than 6%, and fat content is higher than 45%;
Second step: the preparation of rough lacquer tree fat
Adopt the paint seed pulp fraction of non-polar solvent ultrasonic extraction microwave drying, ultrasonic extraction power 50～400W, extract 0～50 ℃ of temperature, extract 10～30min, the volume ratio of paint seed pulp fraction quality and extraction solvent with g/ml count 1: 6～30, extract 1～3 time, after filtering, merge vat liquor, vacuum concentration under 30～60 ℃ of conditions, enriched material is cooled to room temperature, obtains the rough lacquer tree fat of pale green grey;
The 3rd step: the hydrogenation of lacquer tree fat and decoloring reaction
Rough lacquer tree fat is inserted in high-temperature high-pressure reaction kettle, add palladium-carbon catalyst, the charge capacity of palladium-carbon catalyst palladium is 2～10%, and palladium-carbon catalyst consumption is 0.1～1.0% of lacquer tree fat quality, and reactor is warmed up to 70 ℃ of lacquer tree fats and melts completely as liquid state, stirring fully mixes catalyzer, stirring velocity is 60～300rpm, is filled with hydrogen, and controls hydrogen pressure and maintain 0.4～1MPa, 100～160 ℃ of temperature of reaction, reaction times 1～8h;
The 4th step: palladium carbon reclaims
After hydrogenation reaction is complete, filtered while hot, filter residue washs 2～3 times with 1M sodium hydroxide solution at 50～100 ℃, then washes 2～3 times with deionized water, reclaims palladium-carbon catalyst, recycle 4～10 times;
The 5th step: the decolouring of hydrogenation lacquer tree fat
Hydrogenation lacquer tree fat filtrate is maintained the temperature to 50～80 ℃, gac and attapulgite are 1: 1～10 as discoloring agent in mass ratio, discoloring agent and hydrogenation lacquer tree fat crude product mass ratio are 1: 20～200, stir decolouring 10～80min, Plate Filtration, filtrate is put into pallet, naturally cooling, the fine lacquer wax product that preparation whiteness is greater than 90, its acid number and iodine number are less than 10;
The 6th step: fine lacquer wax product whiteness performance measurement
The mensuration of fine lacquer wax product whiteness adopts WSC-S colour examining colour-difference-metre, is adjusted into Hunter system, and preheating 30min, measures its L
*, a
*, b
*, E value, utilize Hunter (hunter) completely whiteness formulas calculate its whiteness (W);
W=100-[(100-L
*)
2+a
*2+b
*2]
1/2
Hunter (Hunter) whiteness of W-fine lacquer wax product sample; L
*-Hunter (Hunter) lightness index; a
*, b
*-Hunter (Hunter) chromaticity index.
2. a kind of preparation method of high-quality fine lacquer wax product according to claim 1, is characterized in that, in the preparation of the rough lacquer tree fat of second step, non-polar solvent is a kind of in the sherwood oil of 60～120 ℃ of boiling points, No. 6 solvent oils, ether, normal hexane, pentane.
3. a kind of preparation method of high-quality fine lacquer wax product according to claim 1, is characterized in that, the charge capacity of the 3rd step palladium-carbon catalyst palladium is preferably 3～7%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110230852.6A CN102329693B (en) | 2011-08-12 | 2011-08-12 | Method for preparing high-quality fine lacquer wax product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110230852.6A CN102329693B (en) | 2011-08-12 | 2011-08-12 | Method for preparing high-quality fine lacquer wax product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102329693A CN102329693A (en) | 2012-01-25 |
| CN102329693B true CN102329693B (en) | 2014-03-05 |
Family
ID=45481662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110230852.6A Expired - Fee Related CN102329693B (en) | 2011-08-12 | 2011-08-12 | Method for preparing high-quality fine lacquer wax product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102329693B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435468A (en) * | 2013-08-26 | 2013-12-11 | 苏勇 | Method for producing stearic acid by utilizing cottonseed oil soapstock |
| CN103849470B (en) * | 2014-03-26 | 2015-04-15 | 云南省轻工业科学研究院 | Preparation method of lacquer tree seed wax oil |
| CN103965780B (en) * | 2014-05-21 | 2016-01-20 | 云南省轻工业科学研究院 | A kind of woodenware lacquer tree fat coating and preparation method thereof |
| HUE040333T2 (en) | 2014-06-04 | 2019-02-28 | Jena Trading Aps | Method and plant for separation of wax and fibers from plants |
| CN105062658B (en) * | 2015-08-06 | 2018-06-19 | 四川凌盾生态农业科技开发有限责任公司 | A kind of green extraction process of lacquer tree fat |
| CN109554232A (en) * | 2018-11-30 | 2019-04-02 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of high-performance novel compounding wax |
| CN113150875B (en) * | 2020-12-30 | 2023-04-07 | 陕西秦乔农林生物科技有限公司 | Low-chroma lacquer wax refining process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205505A (en) * | 2007-12-11 | 2008-06-25 | 中国林业科学研究院林产化学工业研究所 | Extraction method of japan wax, japan wax composite nano material and preparation method |
| CN101348750A (en) * | 2008-08-29 | 2009-01-21 | 中国林业科学研究院资源昆虫研究所 | Decolorizing method of Chinese haze tallow |
| CN101885986A (en) * | 2010-07-16 | 2010-11-17 | 华东理工大学 | Method for refining biological oil |
| CN101906354A (en) * | 2010-08-06 | 2010-12-08 | 中国林业科学研究院林产化学工业研究所 | A kind of method of preparing high-quality colorless lacquer wax quickly by ultraviolet decoloring |
-
2011
- 2011-08-12 CN CN201110230852.6A patent/CN102329693B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205505A (en) * | 2007-12-11 | 2008-06-25 | 中国林业科学研究院林产化学工业研究所 | Extraction method of japan wax, japan wax composite nano material and preparation method |
| CN101348750A (en) * | 2008-08-29 | 2009-01-21 | 中国林业科学研究院资源昆虫研究所 | Decolorizing method of Chinese haze tallow |
| CN101885986A (en) * | 2010-07-16 | 2010-11-17 | 华东理工大学 | Method for refining biological oil |
| CN101906354A (en) * | 2010-08-06 | 2010-12-08 | 中国林业科学研究院林产化学工业研究所 | A kind of method of preparing high-quality colorless lacquer wax quickly by ultraviolet decoloring |
Non-Patent Citations (3)
| Title |
|---|
| 徐三魁.常压低温油脂加氢Pd/C催化剂的研究.《河南工业大学学报(自然科学版)》.2006,第27卷(第6期), * |
| 董艳鹤等.漆蜡的吸附脱色工艺研究.《林产化学与工业》.2011,第31卷(第2期), * |
| 董艳鹤等.漆蜡的提取工艺及其化学成分.《北京林业大学学报》.2010,第32卷(第4期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102329693A (en) | 2012-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102329693B (en) | Method for preparing high-quality fine lacquer wax product | |
| Cheng et al. | Economics of plant oil recovery: A review | |
| CN101906354B (en) | Method for preparing high-quality colorless lacquer wax quickly by ultraviolet decoloring | |
| CN101691520B (en) | Walnut oil refining method | |
| CN103666749A (en) | Processing process for rapeseed oil | |
| CN102766524B (en) | Method for squeezing edible tea seed oil at normal temperature | |
| CN101319168A (en) | Method for preparing wax tree wax with wax tree seed | |
| CN103509651A (en) | Method for extracting ethyl ester enriched fish oil from fish oil refining byproduct | |
| CN101747998A (en) | Method utilizing waste vegetable and animal fat to manufacture candle | |
| CN101411364A (en) | A kind of technique for producing walnut oil by cold pressing and cold refining method | |
| CN104450164A (en) | Method for preparing oil from high-quality rapeseeds with high content of oil under low-temperature and low-moisture conditions | |
| CN103666750A (en) | Refining method of peony seed oil and soapmaking technology | |
| CN107904006A (en) | A kind of high-quality technique for processing walnut oil | |
| CN103451009B (en) | Preparation method of non-edible animal and plant crude oil refined oil | |
| CN111849614A (en) | Preparation method of cosmetic base oil | |
| CN101225345B (en) | Refining method for insect wax | |
| CN104140885B (en) | Oil plant seed is that raw material prepares the method with oxidation resistance long chain fat acid esters | |
| CN102533436A (en) | Method for processing health-care camellia oil | |
| CN103382412B (en) | Preparation process for low-temperature cold-pressed carotene-rich peanut oil | |
| CN108085129B (en) | Preparation method of wood wax oil | |
| CN101177650A (en) | Method for extracting shellac wax and shellac wax prepared by this method | |
| Mantell et al. | Supercritical fluid extraction | |
| CN102326633A (en) | Method for preparing edible oil with high linoleic acid ratio from salt-resistant vegetable seeds | |
| CN108251205A (en) | A kind of giving off a strong fragrance rapeseed oil production technology | |
| CN109181883B (en) | Production process of refined horse oil ethyl ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20120125 Assignee: ZHENJIANG HURUI BIOTECHNOLOGY CO.,LTD. Assignor: INSTITUTE OF CHEMICAL INDUSTRY OF FOREST PRODUCTS, CAF Contract record no.: 2016320000222 Denomination of invention: Method for preparing high-quality fine lacquer wax product Granted publication date: 20140305 License type: Exclusive License Record date: 20161128 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190806 Address after: Room 213, Kechuang Base, No. 3 Hengda Road, Nanjing Economic and Technological Development Zone, Jiangsu Province Patentee after: NANJING ZHONGSEN BIOLOGICAL TECHNOLOGY Co.,Ltd. Address before: Five suojin village Xuanwu District Nanjing 210042 Jiangsu province No. 16 Patentee before: INSTITUTE OF CHEMICAL INDUSTRY OF FOREST PRODUCTS, CAF |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140305 |