CN101402899A - Oxidization fine purification albefaction method for montan wax - Google Patents
Oxidization fine purification albefaction method for montan wax Download PDFInfo
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- CN101402899A CN101402899A CNA2008102335818A CN200810233581A CN101402899A CN 101402899 A CN101402899 A CN 101402899A CN A2008102335818 A CNA2008102335818 A CN A2008102335818A CN 200810233581 A CN200810233581 A CN 200810233581A CN 101402899 A CN101402899 A CN 101402899A
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- Prior art keywords
- wax
- montanin
- montanin wax
- ethyl acetate
- sulphuric acid
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000000746 purification Methods 0.000 title claims description 19
- 239000012170 montan wax Substances 0.000 title claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 230000003647 oxidation Effects 0.000 claims abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 22
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 21
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000001993 wax Substances 0.000 claims description 113
- MKYLOMHWHWEFCT-UHFFFAOYSA-N Manthidine Natural products C1C2=CC=3OCOC=3C=C2C2C3=CC(OC)C(O)CC3N1C2 MKYLOMHWHWEFCT-UHFFFAOYSA-N 0.000 claims description 57
- SNFRINMTRPQQLE-JQWAAABSSA-N Montanin Chemical compound O[C@H]([C@@]1(CO)O[C@H]1[C@H]1[C@H]2O3)[C@]4(O)C(=O)C(C)=C[C@H]4[C@]11OC3(CCCCCCCCCCC)O[C@@]2(C(C)=C)C[C@H]1C SNFRINMTRPQQLE-JQWAAABSSA-N 0.000 claims description 57
- SNFRINMTRPQQLE-OFGNMXNXSA-N Montanin Natural products O=C1[C@@]2(O)[C@@H](O)[C@@]3(CO)O[C@H]3[C@@H]3[C@H]4[C@@]5(C(=C)C)O[C@](CCCCCCCCCCC)(O4)O[C@@]3([C@H](C)C5)[C@@H]2C=C1C SNFRINMTRPQQLE-OFGNMXNXSA-N 0.000 claims description 57
- QTZPBQMTXNEKRX-UHFFFAOYSA-N Voacristine pseudoindoxyl Natural products N1C2=CC=C(OC)C=C2C(=O)C21CCN(C1)C3C(C(C)O)CC1CC32C(=O)OC QTZPBQMTXNEKRX-UHFFFAOYSA-N 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 15
- 238000005238 degreasing Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004061 bleaching Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000006210 lotion Substances 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 241000237502 Ostreidae Species 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 235000020636 oyster Nutrition 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- RMISVBXFFXBNAD-UHFFFAOYSA-N calcium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Ca+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O RMISVBXFFXBNAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
- 239000002253 acid Substances 0.000 abstract description 7
- 239000003077 lignite Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 206010033546 Pallor Diseases 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000021110 pickles Nutrition 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 2
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 description 2
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 2
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 2
- 239000011696 chromium(III) sulphate Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 241001415288 Coccidae Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides an oxidation refined blanching method of lignite wax; coarse lignite wax is used as a material; resin is removed by adopting an ethyl acetate solvent; section oxidation is carried out on the degreased wax by using the mixed liquid of bichromate and sulphuric acid; then acid washing, water washing, drying and shaping are carried out on the oxidized wax to obtain the finished product of refined lignite blanching wax. The Cr<6+> in the oxidation liquid during the oxidation process is basically reduced to Cr<3+>; a tannage liquid can be prepared by carrying out treatment on the oxidation liquid. The production technique of the method is convenient to be operated; the technology can be practical; the cost is low and the practicability is high; and the method can produce a tannage agent needed by the tannage production industry simultaneously when producing the refined lignite wax. Considering from the aspects of environment protection and pollution control, the technique has a realistic meaning.
Description
Technical field
The present invention relates to a kind of oxidization fine purification albefaction method, relate in particular to the oxidization fine purification albefaction method of montanin wax, belong to Coal Chemical Industry, fine chemical technology field.
Background technology
The wax that extracts from brown coal is the unusual complicated mixture of a kind of component, includes thousands of kinds of organic compound, often it is referred to as waxy stone.Because the color of waxy stone is dark, only can be used to make transfer paper, cables etc. do not have the product of particular requirement to color, or as the black rumbling compound of shoe polish, leatherware etc., this demand is little, the dark raw wax that added value is low obviously can not be applied in the product of other industry, makes the range of application of montanin wax be subjected to very big restriction, and then is restricting the montanin wax industrial expansion.With the waxy stone is raw material, and the various light wax that obtains through degreasing, oxide purification, modification upgrading but has very wide applications, and pure wax especially wherein then is the industrial raw material that using value is arranged most.Therefore, separate from brown coal or be refined into pure wax, be the important topic of montanin wax production and research always.
Montanin wax is made light hard wax, is that montanin wax is widened range of application, improves use value, increases the fundamental way of economic benefit.Industrial water vapor distillation under vacuum, nitric acid oxidation method, the chromic salts oxidation style etc. of once adopting are decoloured to it.The distillation method of Shi Yonging is understood decomposes because of wax and be fragmented into small molecules the earliest, so the rate of recovery has only 30%, and complex process.Nitric acid oxidation method can make the nitrated separation of the dark composition of montanin wax, but can not decolour at all, and the rate of recovery is not high, complex process.Chromic acid method and heavy chromic salts method (sodium dichromate 99 or potassium bichromate) are the montanin wax purified best method of generally acknowledging.
The chromic acid method is with chromatosulfuric acid (CrO
3+ H
2SO
4) the oxide purification montanin wax, go back ortho states Cr after the oxidation
+ 3The chromic acid of after electrolysis, regenerating, thus can be recycled.But shortcoming is to consume a large amount of oxygenants, and the electrolyzer of electrolytic regeneration oxidation waste liquid does not have suitable barrier film, electrolytic efficiency is low, current consumption is big, causes total cost to increase.Chinese yunnan is sought the pasture and was built up chromic acid electrolysis production pilot plant in 1978, after the factory transformation reaches 100 tons of/year smart wax scales.Owing to above-mentioned reason, soap stops production.
Basic chromium sulfate is a kind of tanning agent of leather industry consumption maximum, ten thousand tons of the about 8-10 of national annual consumption.Present most of tannery all adopts in acidic medium, with glucose reduction sodium dichromate self-control tanning agent.The disadvantage of this method is that glucose only as the reductive agent completely consumed, is equivalent to waste indirectly grain.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, provide a kind of cost low, practical montanin wax oxidization fine purification albefaction method.
The present invention finishes by following technical proposal: a kind of oxidization fine purification albefaction method of montanin wax, and it is a raw material with the crude montan wax, it is characterized in that through following process steps:
A, with crude montan wax by 4: 1-6: 1 liquid-solid ratio, place ethyl acetate solvent to soak 5～24 hours, under room temperature, extract 2～5 times, each extraction time is 5～24 hours, carry out liquid-solid separation, after solid phase reclaims its residual ethyl acetate solvent, get the degreasing montanin wax; The extraction liquid that is dissolved with the montanin wax resin reclaims ethyl acetate solvent for after recycling through evaporation, and remaining solid substance is the montanin wax resin;
B, by the degreasing montanin wax: the mass ratio of sulphuric acid soln=1: 3～6, it is in 30～70% the sulphuric acid soln that the degreasing montanin wax of above-mentioned A step is joined concentration, behind heat temperature raising to 90 under the agitation condition～110 ℃, press defatted wax again: the mass ratio of dichromate solution=1: 2～3, adding concentration is 40～60% the dichromate aqueous solution, control reaction temperature is 100-120 ℃, stir reaction down 2～4 hours, when the mixed solution color is blackish green, stop heating, be cooled to after wax condenses, reclaim waste reaction solution, make his usefulness in addition, get the oxide purification montanin wax;
It C, with concentration 30～70% sulphuric acid soln by defatted wax: the mass ratio of sulphuric acid soln=1: 2～4, join in the oxide purification montanin wax of above-mentioned B step, behind heat temperature raising to 90 under the agitation condition～110 ℃, press defatted wax again: the mass ratio of dichromate solution=1: 1～2, adding concentration is 40～60% the dichromate aqueous solution, control reaction temperature is 100～120 ℃, reacted under the mechanical stirring 1～2 hour, when the mixed solution color is green, stop heating, be cooled to after montanin wax condenses, reclaim reaction solution; So carry out oxidation bleaching repeatedly, shoaling until the wax product color is faint yellow or oyster white;
D, in the wax of above-mentioned C step gained light colour, press wax: the mass ratio of sulphuric acid soln=1: 2～4 adds concentration and is 10～40% sulphuric acid soln, be heated to 90～110 ℃, agitator treating 0.5～1.0 hour is cooled to room temperature afterwards, washing lotion reclaims and uses, after the wax reheat makes its fusing after washing, add washing 2～3 times, each water consumption is 2～3 times of wax amount, until the pH of water value is 6-7, reclaim washing lotion, drying, moulding get faint yellow or the refining montanin wax finished product of oyster white.
The crude montan wax sheet of described A step is that thickness is the thin slice of 1～4mm, to improve its solubleness and velocity of diffusion in solvent of valchovite.
The dichromate of described B, C step is one or more during sodium dichromate 99, potassium bichromate, calcium bichromate, magnesium bichromate, chromium are done.
The ethyl acetate solvent of described A step adopts the technical grade ethyl acetate solvent.
The extraction liquid phase of described A step is evaporated to conventional evaporation technology of the prior art.
The liquid phase of described B step and C step can be used as oxidation liquid and recycles after reclaiming, and also the ordinary method of available prior art is handled the tanning agent use of back as leather industry.
Because the liquid phase that oxidation generates is sodium chrome alum and vitriolic composition, chrome alum can generate basic chromium sulfate and free sulfuric acid by hydrolysis, for adjusting Cr
2O
3/ total acid concentration ratio adds an amount of Na
2Cr
2O
7.2H
2O and C
6H
12O
6After (glucose) reacts, need to be prepared into the liquid or solid tanning agent product of any basicity (being generally 33-40%) by tannery.
But the washing waste liquid preparating acid washing lotion of described D step recycles, can be in order to preparation Na
2Cr
2O
7The oxidation bleaching reaction solution.
The present invention compared with prior art has following advantage and effect: adopt such scheme, and the first, can effectively deviate from objectionable impurities in the crude montan wax---montanin wax resin, preparation high quality, multiduty defatted wax; The second, valchovite content is low in the defatted wax that this law is produced, and only is 3～5%, the refining montanin wax that it is produced, and of light color, purposes is very wide, can be used for makeup, emulsifying agent, bright dose of throwing, printing, duplicating, automobile and other industries; The 3rd, the waste liquid that is produced in the whole technological process is all recyclable to be recycled, and also can make the Cr in the oxidation liquid
6+Basically all be reduced into Cr
3+, can produce the required tanning agent of leather industry after oxidation liquid handled, do not discharge any contaminating fluid, help environmental protection, extraction process of the present invention is easy and simple to handle simultaneously, technical feasibility, cost is low, practical, can when producing refining wax, go back by-product and go out the essential tanning agent of leather industry, no matter from environmental protection, polluting the control angle considers, still from comprehensive utilization of resources, aspects such as economic benefit consider that the present invention all has important practical significance.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
A, with the crude montan wax thin slice that 100 kilograms of thickness are 1～4mm, place 400 liters of technical grade ethyl acetate solvents to soak 24 hours, extraction is 5 times under room temperature, each extraction time is 24 hours, parting liquid solid phase afterwards, reclaim ethyl acetate solvent residual in the solid phase after, the degreasing montanin wax; The extraction liquid that is dissolved with the montanin wax resin reclaims ethyl acetate solvent for after recycling through evaporation, and remaining solid substance is the montanin wax resin;
B, 50 kilograms of the degreasing montanin waxes of above-mentioned A step are placed in the container of belt stirrer of acidproof lining, add 200 kilograms of concentration and be 50% sulphuric acid soln, heat temperature raising to 110 ℃ under agitation condition, drip 10mlYPSO-1, prevent splash, add 100 kilograms of concentration afterwards and be 50% sodium dichromate aqueous solutio, control reaction temperature is 120 ℃, stirring reaction 2 hours when the mixed solution color is blackish green, stops heating, after treating that wax phase and liquid phase are separated and condensed, emit oxidation mother liquor, be used to produce tanning agent, wax phase is the oxide purification montanin wax;
C, to add concentration in former container be 200 kilograms of 50% sulphuric acid solns, is heated to 110 ℃, adds concentration again and be 50% Na
2Cr
2O
7.2H
2The O70 kilogram reacted 2 hours, repeated this step secondary, carried out oxidation bleaching to montanin wax color and became light yellowly, emitted oxidation mother liquor, was used to produce tanning agent, and wax phase is the oxidation bleaching montanin wax;
D, in the wax of above-mentioned C step gained light colour, add 150 kilograms of concentration and be 30% sulphuric acid soln, be heated to 110 ℃, stir 0.5h, cooling separates wax with pickle solution, be used to prepare oxidation liquid after acid solution reclaims, wax then continues to wash with water, and after heating makes the wax fusing, add washing 3 times, each water consumption is 150 kilograms, until pH=6-7, after washing lotion reclaims, can be recycled, after wax drying, the moulding, get refined bleached wax finished product after washing.
Analytical data:
| Productive rate (%) | Fusing point ℃ | Acid number (mgKOH/g) | Saponification value (mgKOH/g) | pH | Color |
| 83 | 83 | 137 | 163 | 6.7 | Milky white |
Embodiment 2
A, with the crude montan wax thin slice that 100 kilograms of thickness are 1～3mm, place 500 liters of technical grade ethyl acetate solvents to soak 15 hours, extraction is 3 times under room temperature, each extraction time is 15 hours, parting liquid solid phase afterwards, reclaim ethyl acetate solvent residual in the solid phase after, the degreasing montanin wax; The extraction liquid that is dissolved with the montanin wax resin reclaims ethyl acetate solvent for after recycling through evaporation, and remaining solid substance is the montanin wax resin;
B, 50 kilograms of the degreasing montanin waxes of above-mentioned A step are placed in the container of belt stirrer of acidproof lining, add 300 kilograms of concentration and be 30% sulphuric acid soln, heat temperature raising to 90 ℃ under agitation condition, drip 10mlYPSO-1, prevent splash, add 150 kilograms of concentration afterwards and be 40% potassium dichromate aqueous solution, control reaction temperature is 100 ℃, stirring reaction 4 hours when the mixed solution color is blackish green, stops heating, after treating that wax phase and liquid phase are separated and condensed, emit oxidation mother liquor, be used to produce tanning agent, wax phase is the oxide purification montanin wax;
C, to add concentration in former container be 200 kilograms of 30% sulphuric acid solns, be heated to 90 ℃, add concentration again and be 100 kilograms of 40% potassium dichromate aqueous solutions, reacted 1 hour, repeat this step 3 time, carry out oxidation bleaching to montanin wax color and become light yellowly, emit oxidation mother liquor, be used to produce tanning agent, wax phase is the oxidation bleaching montanin wax;
D, in the wax of above-mentioned C step gained light colour, add 200 kilograms of concentration and be 20% sulphuric acid soln, be heated to 100 ℃, stir 1h, cooling separates wax with pickle solution, be used to prepare oxidation liquid after acid solution reclaims, wax then continues to wash with water, and after heating makes the wax fusing, add washing 2 times, each water consumption is 150 kilograms, until pH=6-7, after washing lotion reclaims, can be recycled, after wax drying, the moulding, get refined bleached wax finished product after washing.
Analytical data:
| Productive rate (%) | Fusing point ℃ | Acid number (mgKOH/g) | Saponification value (mgKOH/g) | pH | Color |
| 86 | 81 | 137 | 192 | 6.5 | Milky white |
Embodiment 3
A, with the crude montan wax thin slice that 100 kilograms of thickness are 1～2mm, place 600 liters of technical grade ethyl acetate solvents to soak 5 hours, extraction is 2 times under room temperature, each extraction time is 5 hours, parting liquid solid phase afterwards, reclaim ethyl acetate solvent residual in the solid phase after, the degreasing montanin wax; The extraction liquid that is dissolved with the montanin wax resin reclaims ethyl acetate solvent for after recycling through evaporation, and remaining solid substance is the montanin wax resin;
B, 50 kilograms of the degreasing montanin waxes of above-mentioned A step are placed in the container of belt stirrer of acidproof lining, add 150 kilograms of concentration and be 70% sulphuric acid soln, heat temperature raising to 100 ℃ under agitation condition, drip 10mlYPSO-1, prevent splash, add 125 kilograms of concentration afterwards and be 70% chromium solid carbon dioxide solution, control reaction temperature is 120 ℃, stirring reaction 2 hours when the mixed solution color is blackish green, stops heating, after treating that wax phase and liquid phase are separated and condensed, emit oxidation mother liquor, be used to produce tanning agent, wax phase is the oxide purification montanin wax;
C, to add concentration in former container be 100 kilograms of 70% sulphuric acid solns, be heated to 100 ℃, add concentration again and be 100 kilograms of 70% chromium solid carbon dioxide solution, reacted 2 hours, repeat this step secondary, carry out oxidation bleaching to montanin wax color and become light yellowly, emit oxidation mother liquor, be used to produce tanning agent, wax phase is the oxidation bleaching montanin wax;
D, in the wax of above-mentioned C step gained light colour, add 100 kilograms of concentration and be 70% sulphuric acid soln, be heated to 100 ℃, stir 0.5h, cooling separates wax with pickle solution, be used to prepare oxidation liquid after acid solution reclaims, wax then continues to wash with water, and after heating makes the wax fusing, add washing 3 times, each water consumption is 150 kilograms, until pH=6-7, after washing lotion reclaims, can be recycled, after wax drying, the moulding, get refined bleached wax finished product after washing.
Analytical data:
| Productive rate (%) | Fusing point ℃ | Acid number (mgKOH/g) | Saponification value (mgKOH/g) | pH | Color |
| 81 | 82 | 138 | 180 | 7.0 | Yellow fraction |
Claims (4)
1, a kind of oxidization fine purification albefaction method of montanin wax, it is a raw material with the crude montan wax, it is characterized in that through following process steps:
A, with crude montan wax by 4: 1-6: 1 liquid-solid ratio, place ethyl acetate solvent to soak 5～24 hours, under room temperature, extract 2～5 times, each extraction time is 5～24 hours, carry out liquid-solid separation, after solid phase reclaims residual ethyl acetate solvent, get the degreasing montanin wax; The extraction liquid that is dissolved with the montanin wax resin is after ethyl acetate solvent is reclaimed in evaporation, and remaining solid substance is the montanin wax resin;
B, by the degreasing montanin wax: the mass ratio of sulphuric acid soln=1: 3～6, it is in 30～70% the sulphuric acid soln that the degreasing montanin wax of above-mentioned A step is joined concentration, behind heat temperature raising to 90 under the agitation condition～110 ℃, again by the degreasing montanin wax: the mass ratio of dichromate solution=1: 2～3, adding concentration is 40～60% the dichromate aqueous solution, under 100-120 ℃ of temperature, stirring reaction 2～4 hours, when the mixed solution color is blackish green, stop heating, be cooled to after montanin wax condenses, reclaim waste reaction solution, the oxide purification montanin wax;
It C, with concentration 30～70% sulphuric acid soln by wax: the mass ratio of sulphuric acid soln=1: 2～4, join in the oxide purification montanin wax of above-mentioned B step, behind heat temperature raising to 90 under the agitation condition～110 ℃, press wax again: the mass ratio of dichromate solution=1: 1～2 adds concentration and is 40～60% the dichromate aqueous solution, under 100～120 ℃ of temperature, stirring reaction 1～2 hour is green to the mixed solution color, stops heating, be cooled to after wax condenses, reclaim reaction solution; Oxidation bleaching so repeatedly, shoaling until the wax product color is faint yellow or oyster white;
D, in the wax of above-mentioned C step gained light colour, press wax: the mass ratio of sulphuric acid soln=1: 2～4 adds concentration and is 10～40% sulphuric acid soln, be heated to 90～110 ℃, agitator treating 0.5～1.0 hour is cooled to room temperature afterwards, washing lotion reclaims, after the wax reheat makes its fusing after washing, add washing 2～3 times, each water consumption is 2～3 times of wax amount, until the pH of water value is 6-7, reclaim washing lotion, after wax product drying, the moulding, get faint yellow or the refining montanin wax finished product of oyster white.
2, the oxidization fine purification albefaction method of montanin wax as claimed in claim 1, the crude montan wax that it is characterized in that described A step are that thickness is the thin slice of 1～4mm, to improve its solubleness in ethyl acetate solvent.
3, the oxidization fine purification albefaction method of montanin wax as claimed in claim 1, the dichromate that it is characterized in that described B, C step are one or more during sodium dichromate 99, potassium bichromate, calcium bichromate, magnesium bichromate, chromium are done.
4, the oxidization fine purification albefaction method of montanin wax as claimed in claim 1 is characterized in that the ethyl acetate solvent of described A step adopts the technical grade ethyl acetate solvent.
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| CN103074108A (en) * | 2012-12-07 | 2013-05-01 | 云天化集团有限责任公司 | Degreasing method of crude montan wax |
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