CN102718632A - 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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- CN102718632A CN102718632A CN2012102207638A CN201210220763A CN102718632A CN 102718632 A CN102718632 A CN 102718632A CN 2012102207638 A CN2012102207638 A CN 2012102207638A CN 201210220763 A CN201210220763 A CN 201210220763A CN 102718632 A CN102718632 A CN 102718632A
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- terpine hydrate
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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 the method that Terpine hydrate is produced in a kind of continuous hydration.
Background technology
Terpineol 350 is large spice product; Domestic YO reaches more than 30,000 tons; The aspects such as pore forming material that are widely used in pharmacy, perfumed soap, makeup, mediation essence and flotation non-ferrous metal; Be China's main exit kind, and the sign that increases progressively also appears in export market year by year, export price is also relatively steady always.There is abundant turps resource in China, and annual output is more than 100,000 tons, and its staple is a firpene.The terebinthine main approach that utilizes is exactly synthetic Terpineol 350.
At present, be that the method for raw material production Terpineol 350 mainly contains two kinds of single stage method and two-step approachs with the firpene: single stage method is that firpene direct hydration under the acid catalysis effect generates Terpineol 350; Two-step approach is that firpene takes place earlier to reset hydration generation Terpine hydrate under the acid catalysis effect, and Terpine hydrate generates Terpineol 350 with the diluted acid catalytic dehydration more then.Single stage method and two-step approach are produced Terpineol 350 all respectively has the sorrow shortcoming, but owing to the Terpineol 350 product fragrance of two-step approach gained obviously is superior to the favor that single stage method receives the perfumer.Therefore, two-step approach is the method for the most general present adopted production Terpineol 350.And firpene hydration system Terpine hydrate 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; Just in certain density catalyzer sour water and raw material firpene and the disposable in proportion input reaction kettle of small amounts of emulsifiers; Stirring reaction reacts more than 20 hours usually at a certain temperature, and reaction is discharged sour water again and collected the product Terpine hydrate after finishing.Because hydration reaction needs the water in the consumption acids aqueous solution; So 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 directly be dehydrated into alcohol, and continues dehydration generation terpenes by product, causes yield to descend.Simultaneously, because the hydration reaction time at intermittence is longer, the also corresponding growth of product terpinum hold-time in aqueous acid; Cause the Terpine hydrate crystal of gained older, particle is big, and acid content is high; Make troubles for follow-up dewatering process, and bring problems such as great amount of wastewater and spent acid to production.And; According to the production status analysis, although this hydration reaction belongs to sophisticated traditional technology, still exist following significant disadvantages: 1) hydration yield is not high: the weight yield of firpene hydration reaction system Terpine hydrate is generally about 85% aborning; Reasonable factory; Its Terpine hydrate yield also can only reach about 90%, only is 70% of theoretical yield, bigger improvement is still arranged and improve leeway; 2) processing power is low, and production efficiency is not high.With one 5 cubic metres reaction kettles is example, even by sour water: firpene weight=2:1 feeds intake, and then approximately can drop into 1.6 tons firpene.Because this intermittent type hydration reaction is consuming time longer; Generally need more than 20 hours; And the solid content that reaction finishes in the afterreaction still is high, need take a long time discharge, so each reaction kettle 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 1.5 tons Terpine hydrate; 3) the Terpine hydrate quality of gained is unstable.Because the reaction times is longer, the Terpine hydrate crystal grain is thicker relatively, and wherein contained sour water and oleaginousness change greatly, brings very big inconvenience for follow-up processing and dehydration reaction, not only produces a large amount of waste water, has also therefore increased production cost.
Therefore, people press for to seek and a kind ofly can solve the insufficient new Terpine hydrate working method of intermittent type hydration reaction.Guaranteeing to improve the yield of Terpine hydrate under the condition that next step dehydration reaction can normally be carried out, also just mean the unit consumption that has reduced Terpineol 350, or improved the yield of Terpineol 350.Therefore, production has positive practical significance to Terpineol 350 in this research work.
Summary of the invention
The objective of the invention is to the existing working method of above-mentioned intermittent type hydration system Terpine hydrate and the deficiency of technology, provide a kind of production efficiency height, Terpine hydrate yield height, technology is easy, pollution-free, production cost is lower continuous hydration to produce the method for Terpine hydrate.
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): drop into the aqueous acid and the raw material of specified quantity in the reaction kettle, and heated and stirred;
Step 3): keep temperature of reaction kettle at 25 ~ 35 ℃;
Step 4): react after 5-15 hour, begin to add continuously the production operation of raw material and water, continuous extraction Terpine hydrate and chilli oil, the sour water concentration in the maintenance reaction kettle 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 the 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 by weight being sour water: raw material=1.5 ~ 4:1.
Further, in step 4), the speed that continuously feeding adds raw material is 70 ~ 150 kilograms/hour; The water yield that adds 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), sour water concentration is 25 ~ 35% in the maintenance reaction kettle, and the part by weight of sour water and chilli oil is at 1.5 ~ 4:1 in the maintenance reaction kettle.
The present invention develops on the basis of the reaction mechanism of research firpene hydration reaction and the major and minor product of analysis; In entire reaction course, adopt the mode of continuously feeding and continuous discharging, add raw material and the water that consumes because of reaction, Terpine hydrate and chilli oil that successive extraction reaction simultaneously generates through successive; And through controlling the relation of additional amount and produced quantity; Come sour water concentration and the quantity of sour water and chilli oil in the conditioned reaction still, they are maintained in the middle of certain numerical value, thereby improve reaction efficiency; Reduce the generation of by product, reduce production costs.Concrete, producing Terpine hydrate technology with existing intermittent type hydration process and compare, the present invention has the following advantages:
1) production efficiency is high; The present invention adopts the mode of the continuous discharging of continuously feeding to carry out hydration; Usage ratio of equipment is significantly improved, and the also corresponding raising of production efficiency is an example with one 5 cubic metres reaction kettles; Day produce Terpine hydrate and can reach 2 tons, improved more than 30% than traditional batch formula hydration process;
2) the Terpine hydrate yield is high; The present invention adopts the mode of the continuous discharging of continuously feeding to carry out hydration; In reaction process,, reaction is carried out towards positive dirction, so the yield of Terpine hydrate improve in time the product Terpine hydrate extraction from reaction kettle that generates; Reach 100%, improved 10% than traditional batch formula hydration process;
3) the Terpine hydrate quality of gained is good and stable; Because the present invention adopts the mode of the continuous discharging of continuously feeding to carry out hydration; Just begin the extraction Terpine hydrate in reaction after 5-15 hour, so the Terpine hydrate crystal of gained is tiny, sour water with which and chilli oil amount are few and change less; Terpine hydrate need not to add the alkali adjusting just can directly be used for dehydration reaction, and aftertreatment simply and not produces sewage;
4) production technique is easy, pollution-free;
5) because production efficiency of the present invention yield high, Terpine hydrate is also high, greatly reduce production cost.
Embodiment
Embodiment 1
1) compound concentration is 25% aqueous sulfuric acid;
2) drop into aqueous sulfuric acid and 1.908 tons of turps of 2.85 tons 25% concentration in 5 cubic metres the reaction kettle, and heated and stirred;
3) in whole continuous hydration production process, keep temperature of reaction kettle at 25 ~ 35 ℃;
4) reaction began to carry out continuously feeding, the production operation of discharging continuously after 15 hours.In beginning continuously feeding continuous discharging first day adds 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% altogether; Added 2.243 tons of raw pine fuel-economizings and 0.745 ton of water in second day altogether, 2.432 tons of Terpine hydratees of extraction and 0.564 ton of chilli oil, sour water concentration average out to 28.1%; Added 2.446 tons of raw pine fuel-economizings and 0.802 ton of water on the 3rd day altogether, 2.535 tons of Terpine hydratees of extraction and 0.547 ton of chilli oil, the sour water mean concns is 28.4%; Added 2.156 tons of raw pine fuel-economizings and 0.688 ton of water on the 4th day altogether, 2.371 tons of Terpine hydratees of extraction and 0.684 ton of chilli oil, the sour water mean concns is 28.2%; Added 2.137 tons of raw pine fuel-economizings and 0.684 ton of water on the 5th day altogether, 2.396 tons of Terpine hydratees of extraction and 0.524 ton of chilli oil, the sour water mean concns is 27.8%;
5) reaction finishes, and discharges the material in the still, gets 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) drop into sulfuric acid and phosphate aqueous solution and 1.48 tons of turps of 28.2% of 2.93 tons in 5 cubic metres the reaction kettle, and heated and stirred;
3) in whole continuous hydration production process, keep temperature of reaction kettle at 25 ~ 35 ℃;
4) reaction began to carry out continuously feeding, the production operation of discharging continuously after 10 hours.In beginning continuously feeding continuous discharging first day adds 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% altogether; Added 2.211 tons of raw pine fuel-economizings and 0.785 ton of water in second day altogether, 2.236 tons of Terpine hydratees of extraction and 0.474 ton of chilli oil, sour water concentration average out to 30.7%; Added 2.087 tons of raw pine fuel-economizings and 0.744 ton of water on the 3rd day altogether, 2.205 tons of Terpine hydratees of extraction and 0.486 ton of chilli oil, the sour water mean concns is 30.2%; Added 2.213 tons of raw pine fuel-economizings and 0.652 ton of water on the 4th day altogether, 2.304 tons of Terpine hydratees of extraction and 0.605 ton of chilli oil, the sour water mean concns is 30.6%; Added 2.182 tons of raw pine fuel-economizings and 0.656 ton of water on the 5th day altogether, 2.244 tons of Terpine hydratees of extraction and 0.498 ton of chilli oil, the sour water mean concns is 30.8%;
5) reaction finishes, and discharges the material in the still, gets 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) compound concentration is 30.4% aqueous sulfuric acid;
2) drop into aqueous sulfuric acid and 1.54 tons of firpenes of 30.4% of 3.42 tons in 5 cubic metres the reaction kettle, and heated and stirred;
3) in whole continuous hydration production process, keep temperature of reaction kettle at 25 ~ 35 ℃;
4) reaction began to carry out continuously feeding, the production operation of discharging continuously after 8 hours.In beginning continuously feeding continuous discharging first day adds 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% altogether; Added 2.354 tons of raw material firpenes and 0.712 ton of water in second day altogether, 2.497 tons of Terpine hydratees of extraction and 0.498 ton of chilli oil, sour water concentration average out to 32.0%; Added 2.445 tons of raw material firpenes and 0.925 ton of water on the 3rd day altogether, 2.536 tons of Terpine hydratees of extraction and 0.528 ton of chilli oil, the sour water mean concns is 32.2%; Added 2.234 tons of raw material firpenes and 0.821 ton of water on the 4th day altogether, 2.312 tons of Terpine hydratees of extraction and 0.465 ton of chilli oil, the sour water mean concns is 32.3%; Added 2.352 tons of raw material firpenes and 0.816 ton of water on the 5th day altogether, 2.458 tons of Terpine hydratees of extraction and 0.513 ton of chilli oil, the sour water mean concns is 32.4%;
5) reaction finishes, and discharges the material in the still, gets 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 above is merely the present invention embodiment preferably, only is used to explain the present invention, can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that all any modifications of within spirit of the present invention and principle, being made, be equal to replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
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): drop into the aqueous acid and the raw material of specified quantity in the reaction kettle, and heated and stirred;
Step 3): keep temperature of reaction kettle at 25-35 ℃;
Step 4): react after 5-15 hour, begin to add continuously the production operation of raw material and water, continuous extraction Terpine hydrate and chilli oil, the sour water concentration in the maintenance reaction kettle 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 the 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: step 2) in, raw material is turps or firpene.
5. the method for Terpine hydrate is produced in continuous hydration according to claim 1, it is characterized in that: step 2) sour water of described input and raw material be by weight being sour water: raw material=1.5-4:1.
6. the method for Terpine hydrate is produced in continuous hydration according to claim 1, it is characterized in that: in the step 4), the speed that continuously feeding adds raw material be the 70-150 kilogram/hour.
7. the method for Terpine hydrate is produced in described continuous hydration according to the arbitrary claim of claim 1-6, it is characterized in that: in the step 4) water yield that adds 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.
8. the method for Terpine hydrate is produced in described continuous hydration according to the arbitrary claim of claim 1-6, it is characterized in that: in step 4), keep in the reaction kettle sour water concentration at 25-35%.
9. the method for Terpine hydrate is produced in described continuous hydration according to the arbitrary claim of claim 1-6, it is characterized in that: the part by weight that keeps sour water and chilli oil in the reaction kettle is at 1.5-4:1.
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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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| CN201210220763.8A CN102718632B (en) | 2012-06-29 | 2012-06-29 | Method for preparing terpin hydrate by virtue of continuous hydration |
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| CN102718632A true CN102718632A (en) | 2012-10-10 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966860A (en) * | 2017-04-19 | 2017-07-21 | 福建森美达生物科技有限公司 | The Green production method of terpini hydras and terpinol |
| 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)
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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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- 2012-06-29 CN CN201210220763.8A patent/CN102718632B/en active Active
Patent 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 |
Non-Patent Citations (2)
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| 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》, vol. 34, no. 4, 31 December 2000 (2000-12-31), pages 3 - 6 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966860A (en) * | 2017-04-19 | 2017-07-21 | 福建森美达生物科技有限公司 | The Green production method of terpini hydras and terpinol |
| 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 |
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| CN102718632B (en) | 2014-07-16 |
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