CN102718632B - Method for preparing terpin hydrate by virtue of continuous hydration - Google Patents
Method for preparing terpin hydrate by virtue of continuous hydration Download PDFInfo
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- CN102718632B CN102718632B CN201210220763.8A CN201210220763A CN102718632B CN 102718632 B CN102718632 B CN 102718632B CN 201210220763 A CN201210220763 A CN 201210220763A CN 102718632 B CN102718632 B CN 102718632B
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Abstract
The invention discloses a method for preparing terpin hydrate by virtue of continuous hydration. The method is characterized by comprising the following steps of: under the conditions of certain acidity, temperature and acid water quantity, carrying out the continuous hydration on turpentine or pinene utilized as a raw material in a way of continuously feeding and discharging; and controlling the reaction temperature by adjusting the acid water concentration and the quantity of the acid water and red oil according to the detection data and the weight of materials, thus obtaining the terpin hydrate. Compared with the traditional intermittent hydration method, the method can be used for improving the production efficiency of the terpin hydrate by more than 30%, achieving the yield of 100% and improving the yield by 10%, and has the advantages of being high in production efficiency and yield, simple and convenient in technology, free from pollution, low in production cost, and the like.
Description
Technical field
The present invention relates to a kind of method of continuous hydration, especially relate to a kind of continuous hydration and produce the method for Terpine hydrate.
Background technology
Terpineol 350 is large spice product, domestic annual production reaches more than 30,000 tons, be widely used in the aspects such as the pore forming material of pharmacy, perfumed soap, makeup, mediation essence and flotation non-ferrous metal, it is China's main exit kind, and the sign increasing progressively also appears in export market year by year, export price is also always relatively steady.There is abundant turps resource in China, and annual output is more than 100,000 tons, and its main component is firpene.The terebinthine main approach that utilizes is exactly synthetic Terpineol 350.
At present, mainly contain two kinds of single stage method and two-step approachs taking firpene as the method for raw material production Terpineol 350: single stage method is that firpene direct hydration under acid catalysis generates Terpineol 350; Two-step approach is that firpene first occurs to reset hydration generation Terpine hydrate under acid catalysis, and then Terpine hydrate generates Terpineol 350 with diluted acid catalytic dehydration again.Single stage method and two-step approach are produced Terpineol 350 all respectively sorrow shortcoming, but because the Terpineol 350 product fragrance of two-step approach gained is obviously better than single stage method and is subject to perfumer's favor.Therefore, two-step approach is the method for the most general current adopted production Terpineol 350.And firpene hydration Terpine hydrate processed is the committed step that two-step approach is produced Terpineol 350 under acid catalysis, this step all adopts intermittent type hydration mode to carry out at present, namely certain density catalyzer sour water and raw material firpene and a small amount of emulsifying agent in proportion in disposable input reactor, stirring reaction at a certain temperature, conventionally reaction more than 20 hours, is discharged sour water again and is collected product Terpine hydrate after reaction finishes.Because hydration reaction needs the water in the consumption acids aqueous solution, therefore improved several points before the reaction of the concentration ratio of intermittent type hydration sour water after reaction, and the sour water of higher concentration can make terpinum Direct Dehydration become alcohol, and continue dehydration generation terpenes by product, cause yield to decline.Meanwhile, because the hydration reaction time at intermittence is longer, product terpinum is also corresponding growth of hold-time in aqueous acid, cause the Terpine hydrate crystal of gained older, particle is large, and acid content is high, can make troubles to follow-up dewatering process, and bring the problems such as a large amount of waste water and spent acid to production.And, according to production status analysis, although this hydration reaction belongs to ripe traditional technology, but still exist following obvious shortcomings: 1) hydration yield is not high: the weight yield of firpene hydration reaction Terpine hydrate processed is generally in 85% left and right aborning, reasonable factory, its Terpine hydrate yield also can only reach 90% left and right, is only 70% of theoretical yield, still has greater improvement and enhancement leeway; 2) processing power is low, and production efficiency is not high.Taking the reactors of 5 cubic metres as example, even by sour water: firpene weight=2:1 feeds intake, and approximately can drop into the firpene of 1.6 tons.Because this intermittent type hydration reaction is consuming time longer, generally need more than 20 hours, and it is high to react the solid content finishing in rear reactor, need to take a long time discharge, therefore each reactor can only be produced a collection of Terpine hydrate every day, even calculate by 90% weight yield, the throughput of every day is also only less than the Terpine hydrate of 1.5 tons; 3) the Terpine hydrate quality of gained is unstable.Because the reaction times is longer, Terpine hydrate crystal grain is relatively thick, and wherein contained sour water and oleaginousness change greatly, brings very large inconvenience to follow-up processing and dehydration reaction, not only produces a large amount of waste water, has also therefore increased production cost.
Therefore, people are in the urgent need to finding a kind of new Terpine hydrate production method that can solve intermittent type hydration reaction deficiency.Ensureing, under the condition that next step dehydration reaction can normally be carried out, to improve the yield of Terpine hydrate, also just mean the unit consumption that has reduced Terpineol 350, or improved the yield of Terpineol 350.Therefore, this research work is produced and is had positive practical significance Terpineol 350.
Summary of the invention
The object of the invention is to for the existing production method of above-mentioned intermittent type hydration Terpine hydrate processed and the deficiency of technique a kind of provide that production efficiency is high, Terpine hydrate yield is high, simple process, the continuous hydration that pollution-free, production cost is lower are produced Terpine hydrate method.
For achieving the above object, technical scheme proposed by the invention is: the method for Terpine hydrate is produced in a kind of continuous hydration, it is characterized in that: comprise the steps:
Step 1): the preparating acid aqueous solution;
Step 2): toward the aqueous acid and the raw material that drop into specified quantity in reactor, and heated and stirred;
Step 3): maintain temperature of reaction kettle at 25 ~ 35 DEG C;
Step 4): react after 5-15 hour, start to add continuously the production operation of raw material and water, continuously extraction Terpine hydrate and chilli oil, the sour water concentration in maintenance reactor and the weight ratio of sour water and chilli oil are stable;
Step 5): after reaction finishes, discharge Terpine hydrate, chilli oil and sour water in still.
Further, in step 1), the concentration of aqueous acid is 25 ~ 35%, and acid is the nitration mixture of sulfuric acid or sulfuric acid and phosphoric acid.
Further, in step 2) in, raw material is mainly turps or firpene, and the sour water of input and raw material are sour water: raw material=1.5 ~ 4:1 by weight.
Further, in step 4), it is 70 ~ 150 kgs/hour that continuously feeding adds the speed of raw material; The water yield adding be corresponding period extraction Terpine hydrate weight 20 ~ 40%; The chilli oil weight of extraction be corresponding period extraction Terpine hydrate weight 20 ~ 50%.
Further, in step 4) in, in maintenance reactor, sour water concentration is 25 ~ 35%, and in maintenance reactor, the part by weight of sour water and chilli oil is at 1.5 ~ 4:1.
The present invention is in the reaction mechanism of research firpene hydration reaction and analyzes main, on the basis of by product, develop, in whole reaction process, adopt the mode of continuously feeding and continuous discharge, by the continuous raw material and the water that consume because of reaction added, Terpine hydrate and chilli oil that simultaneously continuous extraction reaction generates, and by controlling the relation of additional amount and produced quantity, regulate sour water concentration in reactor and the quantity of sour water and chilli oil, they are maintained in the middle of certain numerical value, thereby raising reaction efficiency, reduce the generation of by product, reduce production costs.Concrete, compared with existing intermittent type hydration process production Terpine hydrate technique, the present invention has the following advantages:
1) production efficiency is high, the present invention adopts the mode of continuously feeding continuous discharge to carry out hydration, the utilization ratio of equipment is significantly improved, production efficiency is corresponding improve also, taking the reactors of 5 cubic metres as example, day produce Terpine hydrate and can reach 2 tons, improved more than 30% than traditional batch formula hydration process;
2) Terpine hydrate yield is high, the present invention adopts the mode of continuously feeding continuous discharge to carry out hydration, in reaction process in time generate the extraction from reactor of product Terpine hydrate, reaction is carried out towards positive dirction, therefore the yield of Terpine hydrate improves, reach 100%, improved 10% than traditional batch formula hydration process;
3) the Terpine hydrate quality of gained is good and stable, because adopting the mode of continuously feeding continuous discharge, the present invention carries out hydration, after 5-15 hour, just start extraction Terpine hydrate in reaction, therefore the Terpine hydrate crystal of gained is tiny, sour water with which and chilli oil amount are few and change less, Terpine hydrate just can be directly used in dehydration reaction without adding alkali adjusting, and aftertreatment simply and not produces sewage;
4) production technique is easy, pollution-free;
5) because production efficiency of the present invention is high, the yield of Terpine hydrate is also high, greatly reduce production cost.
Embodiment
Embodiment 1
1) aqueous sulfuric acid that compound concentration is 25%;
2) toward the aqueous sulfuric acid and the 1.908 tons of turps that drop into 25% concentration of 2.85 tons in the reactor of 5 cubic metres, and heated and stirred;
3) in whole continuous hydration production process, maintain temperature of reaction kettle at 25 ~ 35 DEG C;
4) reaction, after 15 hours, starts to carry out the production operation of continuously feeding, continuous discharge.At the first day that starts continuously feeding continuous discharge, add altogether 2.684 tons of raw pine fuel-economizings and 0.842 ton of water, 2.984 tons of Terpine hydratees of extraction and 0.653 ton of chilli oil, sour water concentration average out to 27.6%; Within second day, add altogether 2.243 tons of raw pine fuel-economizings and 0.745 ton of water, 2.432 tons of Terpine hydratees of extraction and 0.564 ton of chilli oil, sour water concentration average out to 28.1%; Within the 3rd day, add altogether 2.446 tons of raw pine fuel-economizings and 0.802 ton of water, 2.535 tons of Terpine hydratees of extraction and 0.547 ton of chilli oil, sour water mean concns is 28.4%; Within the 4th day, add altogether 2.156 tons of raw pine fuel-economizings and 0.688 ton of water, 2.371 tons of Terpine hydratees of extraction and 0.684 ton of chilli oil, sour water mean concns is 28.2%; Within the 5th day, add altogether 2.137 tons of raw pine fuel-economizings and 0.684 ton of water, 2.396 tons of Terpine hydratees of extraction and 0.524 ton of chilli oil, sour water mean concns is 27.8%;
5) reaction finishes, and discharges the material in still, obtains 0.812 ton of Terpine hydrate, 1.034 tons of chilli oil and 2.312 tons of sour waters;
This continuous hydration reaction drops into 13.574 tons of raw pine fuel-economizings altogether, obtains 13.53 tons of Terpine hydratees.
Embodiment 2
1) compound concentration is 28.2% sulfuric acid and phosphate aqueous solution;
2) toward 28.2% sulfuric acid and phosphate aqueous solution and the 1.48 tons of turps that drop into 2.93 tons in the reactor of 5 cubic metres, and heated and stirred;
3) in whole continuous hydration production process, maintain temperature of reaction kettle at 25 ~ 35 DEG C;
4) reaction, after 10 hours, starts to carry out the production operation of continuously feeding, continuous discharge.At the first day that starts continuously feeding continuous discharge, add altogether 2.313 tons of raw pine fuel-economizings and 0.752 ton of water, 2.524 tons of Terpine hydratees of extraction and 0.563 ton of chilli oil, sour water concentration average out to 30.5%; Within second day, add altogether 2.211 tons of raw pine fuel-economizings and 0.785 ton of water, 2.236 tons of Terpine hydratees of extraction and 0.474 ton of chilli oil, sour water concentration average out to 30.7%; Within the 3rd day, add altogether 2.087 tons of raw pine fuel-economizings and 0.744 ton of water, 2.205 tons of Terpine hydratees of extraction and 0.486 ton of chilli oil, sour water mean concns is 30.2%; Within the 4th day, add altogether 2.213 tons of raw pine fuel-economizings and 0.652 ton of water, 2.304 tons of Terpine hydratees of extraction and 0.605 ton of chilli oil, sour water mean concns is 30.6%; Within the 5th day, add altogether 2.182 tons of raw pine fuel-economizings and 0.656 ton of water, 2.244 tons of Terpine hydratees of extraction and 0.498 ton of chilli oil, sour water mean concns is 30.8%;
5) reaction finishes, and discharges the material in still, obtains 1.032 tons of Terpine hydratees, 0.986 ton of chilli oil and 2.554 tons of sour waters;
This continuous hydration reaction drops into 12.486 tons of raw pine fuel-economizings altogether, obtains 12.545 tons of Terpine hydratees.
Embodiment 3
1) aqueous sulfuric acid that compound concentration is 30.4%;
2) toward 30.4% aqueous sulfuric acid and the 1.54 tons of firpenes that drop into 3.42 tons in the reactor of 5 cubic metres, and heated and stirred;
3) in whole continuous hydration production process, maintain temperature of reaction kettle at 25 ~ 35 DEG C;
4) reaction, after 8 hours, starts to carry out the production operation of continuously feeding, continuous discharge.At the first day that starts continuously feeding continuous discharge, add altogether 2.508 tons of raw material firpenes and 0.965 ton of water, 2.754 tons of Terpine hydratees of extraction and 0.582 ton of chilli oil, sour water concentration average out to 32.3%; Within second day, add altogether 2.354 tons of raw material firpenes and 0.712 ton of water, 2.497 tons of Terpine hydratees of extraction and 0.498 ton of chilli oil, sour water concentration average out to 32.0%; Within the 3rd day, add altogether 2.445 tons of raw material firpenes and 0.925 ton of water, 2.536 tons of Terpine hydratees of extraction and 0.528 ton of chilli oil, sour water mean concns is 32.2%; Within the 4th day, add altogether 2.234 tons of raw material firpenes and 0.821 ton of water, 2.312 tons of Terpine hydratees of extraction and 0.465 ton of chilli oil, sour water mean concns is 32.3%; Within the 5th day, add altogether 2.352 tons of raw material firpenes and 0.816 ton of water, 2.458 tons of Terpine hydratees of extraction and 0.513 ton of chilli oil, sour water mean concns is 32.4%;
5) reaction finishes, and discharges the material in still, obtains 0.813 ton of Terpine hydrate, 0.822 ton of chilli oil and 3.274 tons of sour waters;
This continuous hydration reaction drops into 13.433 tons of raw material firpenes altogether, obtains 13.37 tons of Terpine hydratees.
The foregoing is only the good embodiment of the present invention, only for explaining the present invention, can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that all any amendments of making within the spirit and principles in the present invention, be equal to replacement and improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. the method for Terpine hydrate is produced in continuous hydration, it is characterized in that: comprise the steps:
Step 1): the preparating acid aqueous solution;
Step 2): toward the aqueous acid and the raw material that drop into specified quantity in reactor, and heated and stirred; The sour water of described input and raw material are sour water: raw material=1.5-4:1 by weight; Described raw material is turps or firpene;
Step 3): maintain temperature of reaction kettle at 25-35 DEG C;
Step 4): react after 5-15 hour, start to add continuously the production operation of raw material and water, continuously extraction Terpine hydrate and chilli oil, in maintenance reactor, sour water concentration is at 25-35%; In maintenance reactor, the part by weight of sour water and chilli oil is at 1.5-4:1; The described water yield adding is the 20-40% of the Terpine hydrate weight of corresponding period extraction; The chilli oil weight of extraction is the 20-50% of the Terpine hydrate weight of corresponding period extraction;
Step 5): after reaction finishes, discharge Terpine hydrate, chilli oil and sour water in still.
2. the method for Terpine hydrate is produced in continuous hydration according to claim 1, it is characterized in that: in step 1), the concentration of aqueous acid is 25-35%.
3. the method for Terpine hydrate is produced in continuous hydration according to claim 1, it is characterized in that: described acid is the nitration mixture of sulfuric acid or sulfuric acid and phosphoric acid.
4. the method for Terpine hydrate is produced in continuous hydration according to claim 1, it is characterized in that: in step 4), it is 70-150 kg/hour that continuously feeding adds the speed of raw material.
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| CN201210220763.8A CN102718632B (en) | 2012-06-29 | 2012-06-29 | Method for preparing terpin hydrate by virtue of continuous hydration |
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| CN106966860B (en) * | 2017-04-19 | 2020-04-24 | 福建森美达生物科技有限公司 | Method for producing terpineol hydrate and terpineol |
| CN113200824A (en) * | 2021-04-07 | 2021-08-03 | 厦门中坤化学有限公司 | Method for synthesizing hydroterpineol in Venturi injection device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102276420A (en) * | 2011-06-22 | 2011-12-14 | 中国林业科学研究院林产化学工业研究所 | Process of preparing terpineol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102276420A (en) * | 2011-06-22 | 2011-12-14 | 中国林业科学研究院林产化学工业研究所 | Process of preparing terpineol |
Non-Patent Citations (4)
| Title |
|---|
| 松节油高得率合成水合萜二醇的研究;赵振东;《林产化工通讯》;20001231;第34卷(第4期);第3-6页 * |
| 水合萜二醇催化脱水制松油醇的研究;陈小鹏;《广西化工》;19921231;第21卷(第3期);第4-6,19页 * |
| 赵振东.松节油高得率合成水合萜二醇的研究.《林产化工通讯》.2000,第34卷(第4期),第3-6页. |
| 陈小鹏.水合萜二醇催化脱水制松油醇的研究.《广西化工》.1992,第21卷(第3期),第4-6,19页. |
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Denomination of invention: Method for preparing terpin hydrate by virtue of continuous hydration Effective date of registration: 20200513 Granted publication date: 20140716 Pledgee: Bank of China Limited Yongan Branch Pledgor: FUJIAN SUMMIT BIOTECHNOLOGY Co.,Ltd. Registration number: Y2020350000028 |