CN104356946A - Method for leaching rosin and heavy oil by crushing rosin residues - Google Patents
Method for leaching rosin and heavy oil by crushing rosin residues Download PDFInfo
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- CN104356946A CN104356946A CN201410561769.0A CN201410561769A CN104356946A CN 104356946 A CN104356946 A CN 104356946A CN 201410561769 A CN201410561769 A CN 201410561769A CN 104356946 A CN104356946 A CN 104356946A
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Abstract
The invention discloses a method for leaching rosin and heavy oil by crushing rosin residues. The rosin and the heavy oil are obtained by crushing the rosin residues into 10-100 meshes, adding an organic solvent, heating, leaching, filtering, distilling at the reduced pressure, distilling at the reduced temperature through a CO2 circulation live air method, and distilling in steam. The rosin residues are crushed, dimethyl carbonate, and petroleum ether and solvent oil 200 are used as leaching solvents, so that the crushed rosin residues are efficiently utilized to leach the rosin and turpentine, the yield of extraction of a traditional rosin residue extraction method is increased from 4.5% to 20%-45%, and the use value and the economic benefit of the rosin residues are greatly increased.
Description
Technical field
The present invention relates to the technical field that pine gum processing process reclaims oil content, particularly a kind of method pulverizing rosin residue solvent leaching rosin and heavy oil.
Background technology
Rosin is a kind of secretory product flowed out by scarfing on pine tree trunk.Containing impurity such as pine sawdust, bark and pine needles in the scrape of pine gum processing pension parachute, scrape melts through heating, cross and filter impurity, then through clarification, fractionation by distillation can obtain rosin and turps two portions.The main composition of rosin is resinous acid, and resinous acid is the general name of a class mixture, is the monocarboxylic acid containing two double bonds with the luxuriant and rich with fragrance skeleton of three rings.Have two chemical reaction centers in resinous acid molecule: double bond and carboxyl, the existence in these two active centre makes rosin have the reactions such as isomerization, addition, disproportionation, hydrogenation, polymerization, ammonia solution, esterification.Many modified products of rosin and the preparation of various derivative are all realized by these reactions, and modified product can be used for the aspects such as sizing agent, coating, ink, pigment, softening agent, rubber industry.Turps mainly consists of monoterpene, and heavy turpentine is mainly sesquiterpene, is mainly α-pinene in monoterpene, and the double bond in firpene and ring can carry out multiple reaction, and the product obtained plays an important role at foodstuffs industry, cosmetics of everyday use, medicine industry, perfume industry.In China's Pinus massoniana Lamb heavy turpentine, main component is longifolene, β-caryophyllene, and both structures are very flexible, easily cytoskeleton rearrangement occur.Longifolene, it has banksia rose smell, is a kind of fabulous cheap raw material of synthetic perfume, is widely used in the synthesis of longifolene ester, longifolane ketone, the banksia rose system spices such as alkanol that come into leaves.The content of β-caryophyllene in Chinese Pinus massoniana Lamb heavy turpentine is less than longifolene, and similar to longifolene, flexible structure, obtains epoxide through hydrogen peroxide oxidation, obtains the source that caryophyllenol is piper nigrum, heart, spearmint oil fragrance after open loop.
In the last few years, because rosin, rosin, turps and deep processed product thereof are more and more, consumption is increasing, and at present can the pine forest area of resin tapping in the progressively reason such as atrophy, rosin price is raised to 12000 Yuan ∕ ton ~ 20000 yuan/ton from 4000 Yuan ∕ ton ~ 6000 Yuan ∕ tons, and the price of rosin remains on a high position for 18000 Yuan ∕ ton ~ 25000 Yuan ∕ tons especially.Therefore carry out the research of solvent leaching rosin oil content from rosin residue, to the comprehensive utilization improving rosin residue, there is important economic worth and social benefit.
Because the rosin being delivered to workshop from storage fat pond is semi-fluid shape, containing impurity such as silt, bark, wood chip, water, appropriate turps (middle oil), water and oxalic acid must be added and be heated to 93 ~ 95 DEG C.Fat liquid after melting flows through skim gate and removes most of impurity, and after melting 3 ~ 4 still rosin, scarfing cinder once, with the rosin in lively atmosphere winding-up residue and turps before scarfing cinder.Whether the composition of rosin residue melts completely different with rosin, melt rosin residue again after high-temperature water vapor (lively atmosphere) blows and carries and reclaim rosin and turps, the grease that in production, control residue surface is contained and effective ingredient, for being less than 5%, then just melting pot to discharge from rosin and discard.As can be seen here, grease composition is contained seldom in rosin residue surface, and such residue is put into boiler combustion as solid waste and fallen by general factory, causes the larger wasting of resources, also reduces the utility value of rosin residue.
China Patent No. 200610018823.2 discloses a kind of method utilizing natural pine gum and rosin factory residue waste liquid to produce rosin, adopts steaming process, by dissolvings, coarse filtration, leaves standstill, clarification, filters distillation waste residue, distills filtrate, finished product packing operation.Common rosin processing basis increases terebinthine consumption, is 0.3 ~ 1.5 times of raw material weight.In common dissolving pan, add liner type filtration unit, to reach the object of sharp separation impurity in whole technical process, its effective ingredient yield reaches 90%.Because indication effective ingredient is the grease that rosin residue surface adsorption content is less than 5%, that is the oil content reclaimed in rosin residue can not higher than 4.5%, i.e. 5% × 90%=4.5%.
China Patent No. 20081010697.4 discloses one and utilizes rosin factory residue devil liquor recovery rosin, terebinthine method, the thick liquid containing rosin, moisture and impurity of discharging in clarification operation when raw material residue waste liquid is steaming process rosin production, also known as middle-layer resin liquid.This invented technology is steaming process, and operation is: dissolve, leave standstill, clarification, filter-press residues thing, distillation, finished product packing.Plate and frame(type)filter press is adopted in filter-press residues thing operation, the method effective ingredient yield is used to reach more than 96%, because indication effective ingredient is the grease that rosin residue surface adsorption content is less than 5%, that is the oil content reclaimed in rosin residue can not higher than 4.5%, i.e. 5% × 90%=4.5%.
China Patent No. 97110438.7 discloses rosin producing method using pine gum residue, comprising: join oil and dissolve, precipitate deslagging, pickling, precipitate and separate and distillation process.Turps is equipped with by they heating for dissolving in dissolving pan in residue, lysed fat liquid puts into the thick slag of setting tank precipitation venting, the fat liquid removing thick slag carries out pickling with oxalic acid diluent again in pickling tank, pickle solution precipitates and isolates fine impurity and oxalic acid diluent, and its fat liquid obtains rosin through distillation.Although the method utilizes the rosin residue melting workshop section, but because residue particles is larger, turps cannot enter the inside of residue particles by oil content stripping, only can obtain the rosin part of residue particles appearance, and the rosin oil content that residue particles inside is contained is not recycled utilization.And with turps to when carrying out dissolving extraction without the residue pulverized, because the outside turps concentration of residue particles is greater than the concentration of granule interior, thus the turps that residue particles inside is contained cannot be extracted, therefore when turps original in raw material is few, with turps not easily by the turps lixiviate in slag out, to make in slag residual more turps on the contrary.
Summary of the invention
The object of the invention is the deficiency proposed for aforesaid method, provide a kind of with the rosin residue melting workshop section for raw material, obtain the method for heavy oil by solvent leaching and Distillation recovery rosin after crushed simultaneously.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions:
From rosin residue, leach the method for rosin and heavy oil, comprise following processing step:
(1) rosin residue is crushed to 10 ~ 100 orders, obtains rosin residue particle;
(2) in rosin residue particle, add organic solvent heating leaching, gained leaching liquid is rosin solution; The weight ratio of rosin residue and organic solvent is 1:1 ~ 16, and described organic solvent is one or more mixture of methylcarbonate, sherwood oil and No. 200 solvent oils;
(3) filtered by rosin solution, gained filtrate carries out underpressure distillation, controls distillation temperature, when absence of liquid steams, stops distillation, obtain grease when gas phase temperature starts to decline; The weight percentage that oil yield accounts for residue total amount is 20% ~ 40%, and described grease is glassy yellow thick liquid, has aromatic odour;
(4) by grease obtained through CO
2the underpressure distillation of circulation lively atmosphere method, it is distillation end point that effluent liquid steams when speed is less than 5/min, and collecting 200 DEG C of front-end volatiles is heavy oil, and its main component is longifolene, and content is 50% ~ 90%, and in still kettle, remaining ingredient is rosin; Or by grease obtained through steam distillation, the heavy oil steamed and the mixing steam of water collect heavy oil after condensing cooling and oily water separation, its main component is longifolene, and content is 50% ~ 90%, and in still pot, remainder is rosin.
The temperature of the above heating leaching is for 25 DEG C to the organic solution atmospheric boiling point temperature of adding.
The above heating leaching time is 0.5 ~ 8h.
The vacuum tightness of the above step (3) underpressure distillation is 0.01 ~ 0.1MPa.
The vacuum tightness of the above step (4) underpressure distillation is 0.06 ~ 0.09MPa.
By grease obtained through CO
2the underpressure distillation of circulation lively atmosphere method, collecting 185 DEG C of front-end volatiles is heavy oil, and in still kettle, remaining ingredient is rosin.
The above step (4) steam distillation temperature is 185 ~ 200 DEG C.
After the above step (3) stops distillation, remaining filter residue water vapor blows to be carried, and reclaims through condensation and oily water separation the organic solvent remained on filter residue.
In the present invention, rosin residue derives from gum resin and deep processed product manufactory thereof, and other reagent is commercially available prod.
Compared with prior art, the invention has the beneficial effects as follows:
1. the present invention make use of the rosin residue leaching rosin and heavy oil that melt workshop section efficiently, brings up to 20% ~ 45%, considerably increase use value and the economic benefit of rosin residue from the oil yield 4.5% of traditional rosin residue extracting method.The factory of an annual output 10000 tons of rosin, annual discharge rosin residue 625 tons, then recyclable about 200 tons of rosin oil contents, if with 12000 yuan/ton ~ 20000 yuan/ton calculating of rosin market value, the value that the rosin oil content reclaimed from rosin residue can be created is 2,400,000 yuan/year ~ 4,000,000 yuan/year.
2. the grease contained due to residue surface is less than 5%, prior art all cannot find the method improving its oil recovery rate, the present invention studies discovery, melts rosin residue weight content composition to be completely: rosin 25%, turps 6%, impurity 35%, moisture 34%, rosin residue inside is full of rosin oil content, and through experiment, pulverizing rosin residue being undertaken measuring its oleaginousness by apparatus,Soxhlet's is 20% ~ 40%, therefore by pulverizing the method for residue, leach more rosin and heavy oil product.
3. the present invention adopts methylcarbonate, sherwood oil, one or more mixture of No. 200 solvent oils is extracting solvent, and inner for residue turps can be leached out, rosin and heavy oil product yield improve 5 ~ 10 times.
Accompanying drawing explanation
Fig. 1 is present invention process schematic flow sheet.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to the scope that embodiment represents.
Embodiment 1:
(1) get rosin residue, pulverizer is crushed to 10-50 order;
(2) by the rosin residue after pulverizing, add methylcarbonate by the weight ratio of 1:1, leach 0.5h at 25 DEG C, gained leaching liquid is rosin solution;
(3) rosin solution is filtered, the underpressure distillation under vacuum tightness 0.01MPa of gained filtrate, control distillation temperature, when absence of liquid steams, stop distillation when gas phase temperature declines, reclaim organic solvent and obtain grease simultaneously, grease obtained is glassy yellow thick liquid, have aromatic odour, it is 30.19% that oil yield accounts for residue total amount weight percentage; Remaining filter residue water vapor blows to be carried, and reclaims through condensation and oily water separation the organic solvent remained on residue;
(4) by grease obtained through CO
2the underpressure distillation of circulation lively atmosphere method, vacuum tightness is 0.09MPa, and it is distillation end point that effluent liquid steams when speed is less than 5/min, and collecting 185 DEG C of front-end volatiles is turps heavy oil partial, and in still kettle, remainder is rosin.
Embodiment 2:
(1) get rosin residue, pulverizer is crushed to 50-80 order;
(2) by the rosin residue after pulverizing, add sherwood oil by the weight ratio of 1:2, leach 2h at 70 DEG C, gained leaching liquid is rosin solution;
(3) rosin solution is filtered, the underpressure distillation under vacuum tightness 0.05MPa of gained filtrate, control distillation temperature, when absence of liquid steams, stop distillation when gas phase temperature declines, reclaim organic solvent and obtain grease simultaneously, grease obtained is glassy yellow thick liquid, have aromatic odour, it is 34.3% that oil yield accounts for residue total amount weight percentage; Remaining filter residue water vapor blows to be carried, and reclaims through condensation and oily water separation the organic solvent remained on residue;
All the other steps are undertaken by embodiment 1.
Embodiment 3:
(1) get rosin residue, pulverizer is crushed to 80-100 order;
(2) by the rosin residue after pulverizing, add No. 200 solvent oils by the weight ratio of 1:4, leach 8h at 100 DEG C, gained leaching liquid is rosin solution;
(3) rosin solution is filtered, the underpressure distillation under vacuum tightness 0.1MPa of gained filtrate, control distillation temperature, when absence of liquid steams, stop distillation when gas phase temperature declines, reclaim organic solvent and obtain grease simultaneously, grease obtained is glassy yellow thick liquid, have aromatic odour, it is 33.2% that oil yield accounts for residue total amount weight percentage; Remaining filter residue water vapor blows to be carried, and reclaims through condensation and oily water separation the organic solvent remained on residue;
(4) by grease obtained through steam distillation underpressure distillation, vacuum tightness is 0.06MPa, and it is distillation end point that effluent liquid steams when speed is less than 5/min, and collecting 200 DEG C of front-end volatiles is turps heavy oil partial, and in still kettle, remainder is rosin.
Embodiment 4:
(1) get rosin residue, pulverizer is crushed to 10-80 order;
(2) by the rosin residue after pulverizing, add methylcarbonate by the weight ratio of 1:16, leach 2h at 55 DEG C, gained leaching liquid is rosin solution;
(3) rosin solution is filtered, the underpressure distillation under vacuum tightness 0.08MPa of gained filtrate, control distillation temperature, when absence of liquid steams, stop distillation when gas phase temperature declines, reclaim organic solvent and obtain grease simultaneously, grease obtained is glassy yellow thick liquid, have aromatic odour, it is 38.5% that oil yield accounts for residue total amount weight percentage; Remaining filter residue water vapor blows to be carried, and reclaims through condensation and oily water separation the organic solvent remained on residue.
By grease obtained through CO
2the underpressure distillation of circulation lively atmosphere method, vacuum tightness is 0.08MPa, and it is distillation end point that effluent liquid steams when speed is less than 5/min, and collecting 190 DEG C of front-end volatiles is turps heavy oil partial, and in still kettle, remainder is rosin.
Claims (8)
1. pulverize a method for rosin residue leaching rosin and heavy oil, it is characterized in that comprising following processing step:
(1) rosin residue is crushed to 10 ~ 100 orders, obtains rosin residue particle;
(2) in rosin residue particle, add organic solvent heating leaching, gained leaching liquid is rosin solution; The weight ratio of rosin residue and organic solvent is 1:1 ~ 16, and described organic solvent is one or more mixture of methylcarbonate, sherwood oil and No. 200 solvent oils;
(3) filtered by rosin solution, gained filtrate carries out underpressure distillation, controls distillation temperature, when absence of liquid steams, stops distillation, obtain grease when gas phase temperature starts to decline;
(4) by grease obtained through CO
2the underpressure distillation of circulation lively atmosphere method, collecting 200 DEG C of front-end volatiles is heavy oil, and in still kettle, remaining ingredient is rosin; Or by grease obtained through steam distillation, the heavy oil steamed and the mixing steam of water collect heavy oil after condensing cooling and oily water separation, in still pot, remainder is rosin.
2. the method for pulverizing rosin residue leaching rosin according to claim 1 and heavy oil, is characterized in that: the temperature of described heating leaching is for 25 DEG C to the organic solution atmospheric boiling point temperature of adding.
3. the method for pulverizing rosin residue leaching rosin according to claim 1 and heavy oil, is characterized in that: the described heating leaching time is 0.5 ~ 8h.
4. the method for pulverizing rosin residue leaching rosin according to claim 1 and heavy oil, is characterized in that: the vacuum tightness of described step (3) underpressure distillation is 0.01 ~ 0.1MPa.
5. the method for pulverizing rosin residue leaching rosin according to claim 4 and heavy oil, is characterized in that: the vacuum tightness of described step (4) underpressure distillation is 0.06 ~ 0.09MPa.
6. the method for pulverizing rosin residue leaching rosin according to claim 1 and heavy oil, is characterized in that: by grease obtained through CO
2the underpressure distillation of circulation lively atmosphere method, collecting 185 DEG C of front-end volatiles is heavy oil, and in still kettle, remaining ingredient is rosin.
7. the method for pulverizing rosin residue leaching rosin according to claim 1 and heavy oil, is characterized in that: described step (4) steam distillation temperature is 185 ~ 200 DEG C.
8. the method for pulverizing rosin residue leaching rosin according to claim 1 and heavy oil, it is characterized in that: after described step (3) stops distillation, remaining filter residue water vapor blows to be carried, and reclaims through condensation and oily water separation the organic solvent remained on filter residue.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567090A (en) * | 2015-12-28 | 2016-05-11 | 安宁泰丰林化工有限公司 | Production method of ground rosin |
| CN106387309A (en) * | 2016-08-31 | 2017-02-15 | 西安若翰生物饲料有限公司 | High-efficient bio-fermented feed |
| CN106890473A (en) * | 2017-04-26 | 2017-06-27 | 贵州林亚达林化科技有限责任公司 | Distilling apparatus and the method using the device work softening agent |
| CN106916535A (en) * | 2017-04-28 | 2017-07-04 | 南宁市青秀区嘉利林化有限公司 | A kind of method that rosin vacuum distillation fractionates out middle oil |
| CN115820125A (en) * | 2022-12-06 | 2023-03-21 | 旌德县建新林产品有限公司 | Method for secondary reprocessing and extracting rosin waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB673501A (en) * | 1950-05-18 | 1952-06-04 | V D Anderson Co | Extraction of oil from nuts and seeds |
| CN1337431A (en) * | 2001-09-03 | 2002-02-27 | 广西大学 | Ping gum processing potching and distilling method |
| CN101343509A (en) * | 2008-08-20 | 2009-01-14 | 李国鸿 | Pine gum processing method and equipment |
| CN102643611A (en) * | 2012-04-24 | 2012-08-22 | 桂林兴松林化有限责任公司 | High-efficiency energy-saving low-cost high-quality rosin production process and production line equipment |
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2014
- 2014-10-21 CN CN201410561769.0A patent/CN104356946B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB673501A (en) * | 1950-05-18 | 1952-06-04 | V D Anderson Co | Extraction of oil from nuts and seeds |
| CN1337431A (en) * | 2001-09-03 | 2002-02-27 | 广西大学 | Ping gum processing potching and distilling method |
| CN101343509A (en) * | 2008-08-20 | 2009-01-14 | 李国鸿 | Pine gum processing method and equipment |
| CN102643611A (en) * | 2012-04-24 | 2012-08-22 | 桂林兴松林化有限责任公司 | High-efficiency energy-saving low-cost high-quality rosin production process and production line equipment |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567090A (en) * | 2015-12-28 | 2016-05-11 | 安宁泰丰林化工有限公司 | Production method of ground rosin |
| CN106387309A (en) * | 2016-08-31 | 2017-02-15 | 西安若翰生物饲料有限公司 | High-efficient bio-fermented feed |
| CN106890473A (en) * | 2017-04-26 | 2017-06-27 | 贵州林亚达林化科技有限责任公司 | Distilling apparatus and the method using the device work softening agent |
| CN106916535A (en) * | 2017-04-28 | 2017-07-04 | 南宁市青秀区嘉利林化有限公司 | A kind of method that rosin vacuum distillation fractionates out middle oil |
| CN115820125A (en) * | 2022-12-06 | 2023-03-21 | 旌德县建新林产品有限公司 | Method for secondary reprocessing and extracting rosin waste |
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