CN1279071C - Production method of terpene resin - Google Patents
Production method of terpene resin Download PDFInfo
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- CN1279071C CN1279071C CN 200410052420 CN200410052420A CN1279071C CN 1279071 C CN1279071 C CN 1279071C CN 200410052420 CN200410052420 CN 200410052420 CN 200410052420 A CN200410052420 A CN 200410052420A CN 1279071 C CN1279071 C CN 1279071C
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Abstract
The present invention relates to a production method of terpene resin. In the production process, firstly, turpentine carries out polymerization reaction with toluene and aluminium trichloride as catalysts in a reaction kettle; hot water is filled in the mixed products of polymerization reaction for carrying out water washing; catalysts and reaction dirt are expelled through water washing; the washed mixed products of polymerization reaction are distilled; toluene is recovered through the distillation process; in the distillation process, liquid resin and substances which can not participate in reaction, are expelled; terpene resin is obtained; the reaction kettle used by the production method comprises an enamel glass main body and a built-in cooling device which is a stainless steel coil pipe set arranged in the kettle; saturated brine at normal temperature is filled in the coil pipe set. The present invention has the advantages of moderate and uniform reaction, small temperature fluctuation range, stable device running, light product color, energy saving, low production cost and good economic benefit and can enhance yield by 20% and reduce device investments.
Description
Technical field
The present invention relates to a kind of production method of terpine resin.
Background technology
Terpine resin is processed by natural turps, has superperformances such as transparent, nontoxic, neutral, electrical insulating property, hydrophobic, non-crystallizable, the diluted alkaline of anti-diluted acid the, heat-resisting, fast light, anti-aging and bonding force be strong.And various synthetics are had good intermiscibility, be soluble in aromatic hydrocarbon and vegetables oil.Terpine resin is a kind of good tackifier, and thickening property is better than rosin and Abietyl modified thing and petroleum resin etc.; It also is the modifying agent of hot melt material, and it is industrial to be widely used in rubber, plastics, printing ink, coating, tackiness agent, pressure sensitive adhesive, cable, color printing, paint, packing, slushing oil, chewing gum etc.The main raw material of producing terpine resin is a turps, turps is a kind of terpene mixture, it is mainly formed is firpene, wherein α-Pai Xi and beta-pinene reach about 90%, has special chemically reactive, be a kind of excellent solvent, be the important source material of coating, artificial camphor, synthetic perfume, Terpineol 350, medicine industry, beneficiation reagent and other organic synthesis industry.
The existing production sequence and the technical process of terpine resin are, raffinate after earlier turps being carried out rectifying and removes rectifying, add solvent toluene and catalyzer again in the turps after rectifying, carry out water wash procedures at turps and solvent toluene reaction back adding hot water, obtain i.e. 2～3 the molecular firpene oligopolymer of firpene of liquid resin with distilling once more behind the refuse that produces in the catalyzer flush away and the reaction process of draining, just made terpine resin (5 above firpene molecular compositions) after the toluene that liquid resin is included reclaims simultaneously.Adopted this mode and made terpine resin and have following problem, one, during rectifying effectively group dicyclopentadiene alkene and also contain α, beta-pinene about 5% in the raffinate all in raffinate.Make active principle loss 3～5%, and energy consumption is big, also need increase by 1,000,000 yuan of corresponding investments; Its two, during polymerization, turps and solvent drop in the still earlier, drop into catalyzer more in batches, the temperature of reaction fluctuation is big, makes the equipment operation not steady, output is little; Its three, during distillation, use thermal oil that heat is provided, heat-conducting oil system is invested 200,000 yuan, distillation time is long, product color is dark; Rectifying and the heating of washing water also must be used steam boiler; In a word, existing technique process needs bigger investment, energy consumption is big, yield is only had an appointment 70% and the quality of product not good enough.
Through the speech that is the theme with " terpenes " Chinese patent documentation is retrieved as can be known, though the patent formerly and the application that relate to terpine resin are arranged, but be the application of terpine resin or the technical scheme of modification aspect, and the technology that relates to itself manufacturing process operation is found as yet.
Summary of the invention
The problem of solution required for the present invention is how to pass through to improve the technique process of terpine resin, has both improved the overall qualities of terpine resin product and the yield of high-quality terpine resin, and two realizations are energy-saving and cost-reducing and the equipment input is descended.
The problem that solves according to above-mentioned needs has designed a kind of production method of terpine resin, and its production process is:
The first step, turps and toluene, catalyzer aluminum chloride carry out polyreaction in reactor,
Second step, in the mix products of polyreaction, inject hot water and wash, by washing catalyzer and reaction dirt are discharged,
The 3rd step, the polyreaction mix products after the washing is distilled, and toluene is reclaimed, and in still-process, the liquid resin and the material that can not participate in reacting are discharged by still-process, the gained after this time distillation is terpine resin.
Wherein, the ordering in launching of raw material and catalyzer is that toluene and catalyzer aluminum chloride drop in the reactor earlier, slowly drip turps and control reaction temperature then and add until turps at-10～5 ℃; The raw material ratio that adds in the reactor is a weight ratio, and ratio is a turps: toluene: aluminum chloride=120～80: 100～60: 50～80.When washing with hot water, water temperature should be controlled in 70～100 ℃ the interval.
And still-process is divided into two stages, at first the polyreaction mix products after the washing is carried out the one-level distillation, still-process reclaimed toluene when distillation temperature was lower than 145 ℃, and fraction is a toluene, and distillation temperature fraction in the time of 145～180 ℃ is to contain the not toluene of reactant and oligopolymer; Secondly, to carrying out secondary distillation again through the polyreaction mix products after the one-level distillation, distillation temperature is 180 ℃, reduce pressure when being higher than 180 ℃, pressure-controlling is at-1～0Pa, in the secondary distillation process, the rest product fluid resin in the polymerization process and the material that can not participate in reacting are discharged, and according to the requirement of terpine resin softening temperature discharging in 220～240 ℃ the time, the gained behind secondary distillation is terpine resin.
In implementation process, secondary distillation adopts 380 ℃ of superheated vapour heating, and the steam after secondary distillation uses is used for the heating of one-level distillatory, and surplus vapour and water of condensation thereof after the used hot water of water wash procedures is distilled by one-level provide.Design can cut down the consumption of energy significantly like this.
Simultaneously, designed a kind of reactor that uses when producing terpine resin, comprise reactor enamel glass body and refrigerating unit, this refrigerating unit is the stainless steel coil pipe group that is built in the reactor, be loaded with the normal temperature saturated brine in the coil pipe group, the liquid level of the liquid of the participation of splendid attire reaction is higher or lower than the height of coil pipe group in the reactor, and wherein the kettle cover of reactor is all passed in the inlet of stainless steel coil pipe group and outlet.
During polymerization of the present invention, reaction temperature and evenly, the temperature of reaction fluctuation range is little, and equipment operates steadily, and the product colour aufhellung can improve yield 20%.The superheated vapour heating is adopted in distillation, wherein secondary distillation is a superheated vapour, the one-level distillation utilizes the surplus vapour waste heat behind the secondary distillation, washing water heats with surplus vapour and one-level water of condensation, and the employing superheated vapour is a lively atmosphere, shortens distillation time, reduces the blowing temperature, the aufhellung product color reaches 2～No. 3 (iron cobalt method).The integral device investment is saved under 1,200,000 yuan of situations, improves day output 40%.Minimizing equipment drops into, recruitment is few, save the energy, directly reduces production costs, and plays favorable economic benefit.
Description of drawings
Accompanying drawing 1 is the FB(flow block) of prior art; Accompanying drawing 2 is FB(flow block) of the present invention; Accompanying drawing 3 is structural representations of the reactor that uses of the present invention.
Embodiment
Thinking of the present invention is by minimizing operation, reduction the improvement that raw-material requirement reaches technology to be reduced production costs, and improves the yield of high-quality terpine resin and overall qualities.
Below be indefiniteness embodiment of the present invention, concrete data and proportioning can be adjusted in real time and the result is not had key according to practical situation to be influenced.
After at first weighing raw pine fuel-economizing and toluene and catalyzer aluminum chloride are ready to respectively in 100: 80: 6.5 ratio, earlier toluene and catalyzer aluminum chloride are dropped in the reactor, slowly drip turps then, temperature of reaction is controlled at-5～0 ℃, adds back 30 minutes polyreactions until turps and finishes; This stage has been eliminated the rectification process in the conventional processes, adopts industrial toluene to substitute solvent toluene, has promptly reduced by a procedure and has reduced again raw-material requirement, and is significantly energy-saving and cost-reducing.
Inject hot water again in the mix products of gained and wash after finishing polyreaction, hot water gets from the water of condensation of distillation process and with the heating of distillation process waste heat, and temperature is controlled at 100 ℃, by washing catalyzer and reaction dirt is discharged.
Polyreaction mix products after the washing is carried out still-process and is divided into two stages, mainly is by still-process toluene to be reclaimed, and in still-process the liquid resin and the material that can not participate in reacting is discharged.Fs is the one-level distillation, and reclaiming fraction when distillation temperature is lower than 145 ℃ is toluene, and the toluene purity of recovery is higher; Distillation temperature fraction in the time of 145～180 ℃ is to contain the not toluene of reactant and oligopolymer, contains more impurity in the toluene of recovery.The distillatory process is, after reactor is finished the one-level distillation, material after the distillation need be pressed into and carry out secondary distillation in second reactor again, distillation temperature is 180 ℃, reduce pressure when being higher than 180 ℃, pressure-controlling is at-0.1Pa, in the secondary distillation process rest product fluid resin in the polymerization process and the material that can not participate in reacting discharged, and according to the requirement of terpine resin softening temperature discharging in 220～240 ℃ the time, the gained behind secondary distillation is terpine resin.In implementation process, secondary distillation adopts 380 ℃ of superheated vapour heating, and the steam after secondary distillation uses is used for the heating of one-level distillatory, and surplus vapour and water of condensation thereof after the used hot water of water wash procedures is distilled by one-level provide.Utilize superheated vapour to distill heating and eliminated traditional heat-conducting oil heating mode, both shortened heat-up time and improved product quality, reduced facility investment again significantly.
And when polymerization, utilize the reactor after improving, with the heat conduction cover by in moving to outward, being about to traditional external placed type heat conduction cover removes, in reactor body 1, be transformed into built-in coil pipe 2, fill in the dish and put saturated brine to improve thermal capacity and heat transfer efficiency, make solvent and catalyzer, after raw material successively drops in the still, fluctuation in temperature of reaction can be controlled among a small circle, reaction is even, and the reaction times obtains shortening, temperature of reaction is reduced, equipment operates steadily, the product colour aufhellung, and the rate of recovery can improve 20%, both rose to 90% by traditional 70%, because of having eliminated the rectifying program, promptly saved facility investment simultaneously, improved utilization rate of raw materials and day output again and can improve 40%.
Claims (8)
1, a kind of production method of terpine resin is characterized in that the production process of terpine resin is
The first step, turps and toluene, catalyzer aluminum chloride carry out polyreaction in reactor,
Second step, in the mix products of polyreaction, inject hot water and wash, by washing catalyzer and reaction dirt are discharged,
The 3rd step, the polyreaction mix products after the washing is distilled, and toluene is reclaimed by still-process, in still-process, also the liquid resin and the material that can not participate in reacting to be discharged, the gained after this time distillation is terpine resin.
2, the production method of terpine resin according to claim 1 is characterized in that toluene and catalyzer aluminum chloride drop in the reactor earlier, slowly drip turps and control reaction temperature then and add until turps at-10 ℃～5 ℃.
3, the production method of terpine resin according to claim 2 is characterized in that the raw material ratio in the described adding reactor is a weight ratio, and ratio is a turps: toluene: aluminum chloride=120～80: 100～60: 50～80.
4, the production method of terpine resin according to claim 1 is characterized in that stage of washing at described injection hot water, and water temperature is controlled at 70～100 ℃.
5, the production method of terpine resin according to claim 1 is characterized in that described still-process is divided into two stages,
At first the polyreaction mix products after the washing is carried out one-level distillation, still-process reclaimed toluene when distillation temperature was lower than 145 ℃, and fraction is a toluene, and distillation temperature fraction in the time of 145～180 ℃ is to contain the not toluene of reactant and oligopolymer;
Secondly, to carrying out secondary distillation again through the polyreaction mix products after the one-level distillation, distillation temperature is 180 ℃, reduce pressure when being higher than 180 ℃, pressure-controlling is at-1～0Pa, in the secondary distillation process, the rest product fluid resin in the polymerization process and the material that can not participate in reacting are discharged, and according to the requirement of terpine resin softening temperature discharging in 220～240 ℃ the time, the gained behind secondary distillation is terpine resin.
6, the production method of terpine resin according to claim 5, it is characterized in that secondary distillation adopts 380 ℃ of superheated vapour heating, steam after secondary distillation uses is used for the heating of one-level distillatory, and surplus vapour and water of condensation thereof after the used hot water of water wash procedures is distilled by one-level provide.
7, a kind of reactor that uses when producing terpine resin, comprise reactor enamel glass body and refrigerating unit, it is characterized in that described refrigerating unit is the stainless steel coil pipe group that is built in the reactor, be loaded with the normal temperature saturated brine in the coil pipe group, the liquid level of the liquid of the participation of splendid attire reaction is higher or lower than the height of coil pipe group in the reactor.
8, the reactor that uses during production terpine resin according to claim 7 is characterized in that the inlet of stainless steel coil pipe group and the kettle cover that reactor is all passed in outlet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410052420 CN1279071C (en) | 2004-11-21 | 2004-11-21 | Production method of terpene resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410052420 CN1279071C (en) | 2004-11-21 | 2004-11-21 | Production method of terpene resin |
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| CN1631916A CN1631916A (en) | 2005-06-29 |
| CN1279071C true CN1279071C (en) | 2006-10-11 |
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| CN 200410052420 Expired - Fee Related CN1279071C (en) | 2004-11-21 | 2004-11-21 | Production method of terpene resin |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544716B (en) * | 2009-05-04 | 2013-03-20 | 张乃银 | Method and equipment for recycling catalyst in production of terpene resin |
| CN101891862A (en) * | 2010-08-18 | 2010-11-24 | 赣州泰普化学有限公司 | Modified terpene resin and preparation method thereof |
| CN102020734B (en) * | 2010-11-16 | 2012-06-13 | 南京大学扬州化学化工研究院 | Preparation method of sesquiterpene resin |
| CN102382220A (en) * | 2011-08-30 | 2012-03-21 | 广东华林化工有限公司 | Ultralight-colored polyterprene resin production process |
| CN102382221B (en) * | 2011-08-30 | 2014-07-16 | 广东华林化工有限公司 | Phellandrene resin production process |
| CN102633919A (en) * | 2012-05-02 | 2012-08-15 | 中国林业科学研究院林产化学工业研究所 | Terpene resin and preparation method thereof |
| CN102898564B (en) * | 2012-11-01 | 2015-07-22 | 张道飘 | Method for preparing terpene resin |
| CN102964495A (en) * | 2012-11-15 | 2013-03-13 | 梧州市松桦化学品有限公司 | Synthetic method of terpene resin |
| CN104151467A (en) * | 2014-08-21 | 2014-11-19 | 梧州市嘉盈树胶有限公司 | Preparation method of terpene resin |
| CN104910303A (en) * | 2015-05-27 | 2015-09-16 | 梧州市嘉盈树胶有限公司 | Method for preparing terpene resin by using dipentene as raw material |
| CN106519534B (en) * | 2016-12-05 | 2018-09-28 | 罗定市星光化工有限公司 | A kind of production technology of food-grade terpene resin |
| CN109485765A (en) * | 2018-12-07 | 2019-03-19 | 江西瑞源食品科技有限公司 | A kind of new process of terpene resin preparation |
| CN111548439A (en) * | 2020-04-30 | 2020-08-18 | 广东星光脂胶科技股份有限公司 | Production process of terpene resin |
| CN112048032A (en) * | 2020-09-08 | 2020-12-08 | 韶关林和林产科技有限公司 | Preparation method of terpene resin |
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Assignee: Luoding Xingguang Chemical Engineering Co., Ltd. Assignor: Lan Yunquan Contract record no.: 2010440000704 Denomination of invention: Production method of terpene resin Granted publication date: 20061011 License type: Exclusive License Open date: 20050629 Record date: 20100609 |
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Granted publication date: 20061011 Termination date: 20101121 |