CN1105051A - Method for producing disproportionated rosin by using pine gum as raw material - Google Patents
Method for producing disproportionated rosin by using pine gum as raw material Download PDFInfo
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- CN1105051A CN1105051A CN 94108045 CN94108045A CN1105051A CN 1105051 A CN1105051 A CN 1105051A CN 94108045 CN94108045 CN 94108045 CN 94108045 A CN94108045 A CN 94108045A CN 1105051 A CN1105051 A CN 1105051A
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Abstract
The process for direct production of dismutated rosin with pine gum includes such technological steps as dissolving raw pine gum with turpentine (or pinene) or hydrogenized turpentine (or pinane), direct dismutation at lower temp. under action of catalyst, removing catalyst by filter and distillation. Obtained rosin features light colour, high acidic value and quality and low cost.
Description
Disproportionation rosin is important product in the forest chemical (rosin deep processing), and it mainly is that component is dehydroabietic acid (content is 40～60%), dihydroabietic acid and tetrahydroabietic acid.System by rosin at a certain temperature, through palladium charcoal (5%Pd/c) catalyst action, wherein abietic type acid's part molecule is deviate from two hydrogen atoms and is made double-bond rearrangement, it is dehydroabietic acid that the C ring of three ring parent nucleus forms stable benzene ring structure, and the hydrogen atom of deviating from is absorbed by another part abietic type acid, generate dihydroabietic acid and tetrahydroabietic acid, thereby make common rosin obtain the essence improvement because of the easily oxidizable that conjugated double bond caused, thereby stable in properties, easy oxidation discoloration is not subjected to the user and welcomes.In the disproportionation process, dehydrogenation and hydrogenation are to carry out the intermolecular of rosin inside, need not consume extra hydrogen.Its reaction formula is as follows:
The method of traditional with rosin is raw material production disproportionation rosin be earlier with raw resin with turps melt into fat liquid, clarification after filtration,, distillation and make rosin, carry out disproportionation again with the rosin fusion and under the catalysis of palladium or iodine,, require temperature of reaction higher because of the viscosity of molten rosin is big, generally at 250～270 ℃, and under this high temperature, except that disproportionation, also have the side reaction of decarboxylation to take place, the product acid number is reduced, influence use value.At high temperature also have a small amount of rosin to decompose in addition, influence yield, product colour deepens.And full-bodied reaction mass exists the difficulty that is difficult to filtering catalyst, and domestic still do not have suitable filter plant and satisfy this requirement, and therefore up to the present, domestic only have a tame factory to produce disproportionation rosin with import Japan technology and equipment.
The present invention system dissolves the lumps raw resin with turps (or firpene) or hydroterpin (or pinane equal solvent), clarification after filtration again, the fat liquid of the oil-containing 40-80% that makes can directly be used as the disproportionation raw material, after reaction finishes, the elimination catalyzer steams solvent and can obtain the disproportionation rosin product.Saved by fat liquid and made the rosiny process, thereby simplified flow process, the problem of reducing investment outlay and reducing cost and also having avoided repeatedly heat fused that product colour is deepened.Reaction conditions relaxes in addition; only need keep under ammonia (about 0.2MPa) protection 140～180 ℃ (relevant with fat liquid concentration and catalyst activity) and can finish disproportionation in 3～4 hours, the consumption of palladium carbon catalyst (5%Pd/c) is charging capacity 0.2-0.4%.Low-temp reaction has been avoided the generation of decarboxylation side reaction, help the raising of product acid value, low temperature has also avoided the rosiny thermolysis to help improving the color of product simultaneously, and more prior is that low viscosity helps filter operation, uses homemade filter plant to meet the demands.Owing to reduced temperature of reaction, can use steam as heat-transfer medium, do not need thermal oil or electrically heated, cost and investment are descended significantly, as rosin is made rosin earlier, again with turps (or firpene), or hydroterpin (or pinane), or other solvent is made solution, disproportionation under similarity condition then, though the gained disproportionation rosin than being the poor of raw material directly with rosin, but still the nilox resin that makes than scorification is of light color, quality is good, and cost is low.Therefore, the present invention has the application value of reality.
Prepared disproportionation rosin quality of the inventive method and national specialized standard 2BB72002-84(traditional method) contrast as follows:
Claims (4)
1, the present invention be a kind of be the method that raw material is directly made nilox resin with rosin, it is characterized in that utilizing turps in the rosin (or adding hydroterpin or pinane etc. in addition) to make solvent, its advantage is big to resinous acid solubleness, and does not have the incoherent impurity that may bring into when adopting other solvent.The abietic type acid carries out the catalytic disproportionation reaction in solvent.
Reaction formula is:
Abietic type acid's dehydroabietic acid dihydroabietic acid tetrahydroabietic acid.
2, another feature of the present invention is that temperature of reaction is low, has only 140～180 ℃, adopts palladium carbon catalyst (5%Pd/c), and consumption is the 0.2-0.4% of charging capacity
3, key character of the present invention is that to remove by filter the process of catalyzer more or less freely.Do not need to adopt the leaf-type filter of the high import 700 order Stainless Steel Cloths of price.And all can meet the demands with homemade plate-and-frame filter press, filtration device or accurate micropore tubular filter.
4, the invention is characterized in the solvent method disproportionation, therefore produce season at non-rosin, promptly use stock's rosin to be raw material, be dissolved in disproportionation in pinane or other solvent, still low, of light color than scorification disproportionation temperature, quality is good, and cost is low.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108045A CN1035012C (en) | 1994-08-08 | 1994-08-08 | Method for producing disproportionated rosin by using pine gum as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108045A CN1035012C (en) | 1994-08-08 | 1994-08-08 | Method for producing disproportionated rosin by using pine gum as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1105051A true CN1105051A (en) | 1995-07-12 |
| CN1035012C CN1035012C (en) | 1997-05-28 |
Family
ID=5033317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94108045A Expired - Fee Related CN1035012C (en) | 1994-08-08 | 1994-08-08 | Method for producing disproportionated rosin by using pine gum as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1035012C (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317348C (en) * | 2004-09-27 | 2007-05-23 | 广西大学 | Method for producing pale disproportionated rosin with high content dehydroabietic acid and P-camphogen simultinuously |
| CN100358958C (en) * | 2006-03-09 | 2008-01-02 | 古远亮 | Production of rosin from natural pine gum |
| CN100412151C (en) * | 2006-04-17 | 2008-08-20 | 古远亮 | Method for producing colophony by using natural turpentine and residue and waste liquor from colophony production factory |
| CN100453612C (en) * | 2006-05-15 | 2009-01-21 | 古远亮 | Production process of semi-finished rosin with fallen pine resin |
| CN102127369A (en) * | 2010-12-16 | 2011-07-20 | 广东科茂林产化工股份有限公司 | Method for preparing disproportionated rosin |
| CN101642092B (en) * | 2009-06-26 | 2012-09-05 | 深圳诺普信农化股份有限公司 | Green plant source environmental protection solvent and preparation method thereof |
| CN103436175A (en) * | 2013-08-27 | 2013-12-11 | 广西梧州松脂股份有限公司 | Method for increasing content of dehydroabietic acid in disproportionated rosin |
| CN105111940A (en) * | 2015-09-23 | 2015-12-02 | 广西科茂林化有限公司 | Disproportionated rosin and preparation method thereof |
| CN105713523A (en) * | 2016-04-27 | 2016-06-29 | 容县自良宏旺松脂厂 | Method for directly preparing disproportionated rosin from rosin by using non-noble metal as catalyst |
| CN105713522A (en) * | 2016-04-27 | 2016-06-29 | 容县自良宏旺松脂厂 | Disproportionated rosin preparation method with palladium/carbon as catalyst |
| CN105778771A (en) * | 2016-04-27 | 2016-07-20 | 容县自良宏旺松脂厂 | Method for directly preparing disproportionated rosin from rosin through taking iodine as catalyst |
| CN105778768A (en) * | 2016-04-27 | 2016-07-20 | 容县自良宏旺松脂厂 | Method for directly preparing disproportionated rosin from rosin through taking palladium on carbon as catalyst |
| CN106010272A (en) * | 2016-06-03 | 2016-10-12 | 容县自良宏旺松脂厂 | Method for preparing light-color disproportionated rosin by using organic ceramsite decolorising agent |
| CN106010273A (en) * | 2016-06-03 | 2016-10-12 | 容县自良宏旺松脂厂 | Method for preparing light-color disproportionated rosin by using phosphoric acid compound ceramsite decolorising agent |
| CN106010271A (en) * | 2016-06-03 | 2016-10-12 | 容县自良宏旺松脂厂 | Method for preparing disproportionated rosin |
| CN106010276A (en) * | 2016-06-03 | 2016-10-12 | 容县自良宏旺松脂厂 | High-yield and low-cost method for preparing disproportionated rosin |
| CN106010274A (en) * | 2016-06-03 | 2016-10-12 | 容县自良宏旺松脂厂 | Method for preparing light-color disproportionated rosin by using oxalic acid ceramsite decolorising agent |
| CN109321269A (en) * | 2018-09-12 | 2019-02-12 | 广西大学 | The method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8506023D0 (en) * | 1985-03-08 | 1985-04-11 | Enichem Elastomers Ltd | Disproportionation of unsaturated acids |
| JPS6381181A (en) * | 1986-09-22 | 1988-04-12 | Arakawa Chem Ind Co Ltd | Production of heterogeneous |
| US5387669A (en) * | 1991-12-21 | 1995-02-07 | Arakawa Kagaku Kogyo Kabushiki Kaisha | Process for preparing rosin ester and colorless rosin |
-
1994
- 1994-08-08 CN CN94108045A patent/CN1035012C/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317348C (en) * | 2004-09-27 | 2007-05-23 | 广西大学 | Method for producing pale disproportionated rosin with high content dehydroabietic acid and P-camphogen simultinuously |
| CN100358958C (en) * | 2006-03-09 | 2008-01-02 | 古远亮 | Production of rosin from natural pine gum |
| CN100412151C (en) * | 2006-04-17 | 2008-08-20 | 古远亮 | Method for producing colophony by using natural turpentine and residue and waste liquor from colophony production factory |
| CN100453612C (en) * | 2006-05-15 | 2009-01-21 | 古远亮 | Production process of semi-finished rosin with fallen pine resin |
| CN101642092B (en) * | 2009-06-26 | 2012-09-05 | 深圳诺普信农化股份有限公司 | Green plant source environmental protection solvent and preparation method thereof |
| CN102127369A (en) * | 2010-12-16 | 2011-07-20 | 广东科茂林产化工股份有限公司 | Method for preparing disproportionated rosin |
| CN103436175B (en) * | 2013-08-27 | 2016-01-20 | 广西梧州松脂股份有限公司 | Improve the method for nilox resin dehydrogenation abietic acid content |
| CN103436175A (en) * | 2013-08-27 | 2013-12-11 | 广西梧州松脂股份有限公司 | Method for increasing content of dehydroabietic acid in disproportionated rosin |
| CN105111940A (en) * | 2015-09-23 | 2015-12-02 | 广西科茂林化有限公司 | Disproportionated rosin and preparation method thereof |
| CN105713523A (en) * | 2016-04-27 | 2016-06-29 | 容县自良宏旺松脂厂 | Method for directly preparing disproportionated rosin from rosin by using non-noble metal as catalyst |
| CN105713522A (en) * | 2016-04-27 | 2016-06-29 | 容县自良宏旺松脂厂 | Disproportionated rosin preparation method with palladium/carbon as catalyst |
| CN105778771A (en) * | 2016-04-27 | 2016-07-20 | 容县自良宏旺松脂厂 | Method for directly preparing disproportionated rosin from rosin through taking iodine as catalyst |
| CN105778768A (en) * | 2016-04-27 | 2016-07-20 | 容县自良宏旺松脂厂 | Method for directly preparing disproportionated rosin from rosin through taking palladium on carbon as catalyst |
| CN106010272A (en) * | 2016-06-03 | 2016-10-12 | 容县自良宏旺松脂厂 | Method for preparing light-color disproportionated rosin by using organic ceramsite decolorising agent |
| CN106010273A (en) * | 2016-06-03 | 2016-10-12 | 容县自良宏旺松脂厂 | Method for preparing light-color disproportionated rosin by using phosphoric acid compound ceramsite decolorising agent |
| CN106010271A (en) * | 2016-06-03 | 2016-10-12 | 容县自良宏旺松脂厂 | Method for preparing disproportionated rosin |
| CN106010276A (en) * | 2016-06-03 | 2016-10-12 | 容县自良宏旺松脂厂 | High-yield and low-cost method for preparing disproportionated rosin |
| CN106010274A (en) * | 2016-06-03 | 2016-10-12 | 容县自良宏旺松脂厂 | Method for preparing light-color disproportionated rosin by using oxalic acid ceramsite decolorising agent |
| CN109321269A (en) * | 2018-09-12 | 2019-02-12 | 广西大学 | The method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1035012C (en) | 1997-05-28 |
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