CN113200824A - Method for synthesizing hydroterpineol in Venturi injection device - Google Patents
Method for synthesizing hydroterpineol in Venturi injection device Download PDFInfo
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- CN113200824A CN113200824A CN202110374286.XA CN202110374286A CN113200824A CN 113200824 A CN113200824 A CN 113200824A CN 202110374286 A CN202110374286 A CN 202110374286A CN 113200824 A CN113200824 A CN 113200824A
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- pinene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
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Abstract
A method for synthesizing terpene glycol hydrate in a Venturi injection device relates to the hydration of pinene or turpentine to form terpene glycol hydrate under the catalysis of acid. Mixing pinene and sulfuric acid solution via Venturi ejector to react, and adding proper amount of emulsifier peregal and acetic acid. Cooling the container by an internal coil pipe; the oil-water mixed liquid in the container enters a Venturi ejector after being pressurized by a pump to form jet flow, the side face sucks materials and air in a head tank, the two phases form intensive mixing in the Venturi tube and then enter the container, the two phases in the container are cooled and then layered, an upper oil phase overflows and enters a filter, vacuum filtration is formed through the head tank, the oil phase enters the head tank, part of solid particles are left on filter cloth, and after multiple cycles, the reaction reaches the end point; the reaction product is terpineol hydrate, which is an intermediate for producing terpineol; the process method can replace the traditional stirred tank reaction device.
Description
Technical Field
The invention relates to a method for synthesizing hydroterpineol by hydrating pinene or turpentine under the catalysis of acid, in particular to a method for synthesizing hydroterpineol in a Venturi injection device.
Background
Terpineol, also known as terpineol, is a colorless, transparent, viscous liquid, has a lasting lilac fragrance and stable properties, and is an important synthetic perfume. According to different dosage, the product can be used as flavoring agent, printing and dyeing agent, detergent, disinfectant, etc.
The production process of terpineol mainly comprises two steps, namely a two-step method and a one-step method. The two-step method is favorable for the product by a flavoring agent because of the one-step method of the aroma; the key step of the two-step method is to synthesize the terpene glycol hydrate in a reaction kettle by high-speed stirring; stirring at a speed of 600-800 r/min, crushing the oil phase into small droplets, and fully contacting the small droplets with the acid solution, wherein the oil phase and the water phase which are immiscible can react, and the reaction time is generally 22-24 h. And dehydrating the terpene glycol hydrate to obtain the terpineol. The stirring speed in the traditional process is high, the requirement on an industrial device is high, the amplification is limited, only 2-3 cubic reaction kettles are used at present, and large-scale sets of reaction devices are needed for increasing the yield.
Disclosure of Invention
The invention aims to provide a method for synthesizing hydroterpineol in a Venturi injection device, which can generate the hydroterpineol by turpentine or pinene under the catalysis of acid.
The invention comprises the following steps:
1) preparing a sulfuric acid solution in a square groove with a built-in cooling coil, and adding a quantitative emulsifier peregal and a regulator acetic acid solution;
in the step 1), the percentage concentration of the sulfuric acid solution can be 25-30%, and the mass ratio of peregal to pinene is (1-1.5): 1000; the mass ratio of acetic acid to pinene is (1-2): 1000.
2) Quantitative pinene or turpentine is put into the head tank;
in the step 2), the elevated tank can be a raw material tank or a suction filtration solution receiving tank; the mass ratio of pinene or turpentine to sulfuric acid solution is 1: 2.5-3.
3) Starting a pump to pump the acid solution in the square groove into the Venturi ejector and then into the square groove to form a loop;
in the step 3), the flow of the pump is controlled to be 40-60 m3And h, adopting fluorine lining at the overflowing part of the pump.
4) Opening a lateral feed inlet of the Venturi ejector, sucking pinene or turpentine materials in the high-level groove into the Venturi ejector, and supplementing 30-50 m3Air amount per hour;
5) starting a coil pipe, namely cooling water at 0 ℃, and controlling the flow rate to enable the temperature of the solution in the square groove to be 25-30 ℃;
6) after the oil-water two phases enter the square groove, the oil-water two phases are cooled and layered, and the upper oil phase enters the filter through an overflow port;
in the step 6), if crystals are generated, the crystals enter a filter along with the oil phase, and the oil phase enters a head tank for recycling after suction filtration.
7) Sampling an oil phase in the head tank, analyzing the content of pinene or turpentine, stopping the pump and stopping vacuum when the reaction is finished if the content of pinene is 5-7%;
8) the crystal terpene glycol hydrate in the filter is used for the next reaction, and the sulfuric acid solution in the square groove is properly supplemented and recycled.
The invention mixes pinene and sulfuric acid solution through Venturi ejector to react, in order to enhance the oil-water two-phase mixing, add right amount of emulsifier peregal and acetic acid in the solution. Cooling the container by an internal coil pipe; the oil-water mixed liquid in the container enters a Venturi ejector after being pressurized by a pump to form jet flow, the side face sucks materials and air in a head tank, the two phases form intensive mixing in the Venturi tube and then enter the container, the two phases in the container are cooled and then layered, an upper oil phase overflows and enters a filter, vacuum filtration is formed through the head tank, the oil phase enters the head tank, part of solid particles are left on filter cloth, and after multiple cycles, the reaction reaches the end point; the reaction product is terpineol hydrate, which is an intermediate for producing terpineol; the process method can replace the traditional stirred tank reaction device.
The invention aims to replace a high-speed stirring batch reactor in the traditional process, reduce the equipment requirement and equipment investment, can be designed into a continuous production device, and solves the bottleneck that the batch reactor is difficult to produce on a large scale. The invention adopts the jet flow formed by the Venturi jet device to realize the intensive mixing of oil phase and water phase, thereby achieving the purpose of replacing a reaction kettle with high-speed stirring, having the same reaction effect as the reaction kettle, but having low equipment investment, being convenient for expanding production, or being designed to be continuous production. The acid solution can be recycled, and the pollution discharge is reduced.
Drawings
FIG. 1 is a schematic flow diagram of the synthesis of terpene glycol hydrate in a venturi injection device of the present invention.
Detailed Description
The following examples will further illustrate the present invention with reference to the accompanying drawings.
FIG. 1 shows a schematic flow diagram of the synthesis of hydroterpineol in a Venturi jet device according to the present invention. The device in the jet reaction is provided with a high-level tank 1, a filter 2, a square tank 3, a circulating pump 4 and a Venturi ejector 5; elevated tank 1 is connected with venturi sprayer 5, filter 2 and is formed the return circuit, square groove 3, circulating pump 4, venturi sprayer 5 are connected and are formed the return circuit.
The embodiment of the invention comprises the following steps:
1) pinene or turpentine is pumped into a high-level tank 1, a sulfuric acid solution is prepared in a square tank 3, and an emulsifier peregal and acetic acid are added. The mass percentage content of the pinene and the sulfuric acid solution is 1: 2.5-3, the mass ratio of peregal to pinene is (1-1.5) 1000, the mass ratio of acetic acid to pinene is (1-1.5) 1000, and the temperature of the injection reaction is 23-30 ℃.
2) The sulfuric acid solution is introduced into a circulating pump 4 from the bottom of the square groove 3, and is pumped into a Venturi ejector 5 to suck pinene and air laterally.
3) The mixed liquid enters a square groove 3, and the flow of the cooling liquid of the inner coil is controlled, so that the temperature of the materials in the groove is kept at 23-30 ℃. After the oil phase and the water phase are layered, the upper oil phase enters a filter 2, generated crystals are left in the filter after suction filtration, and the oil phase returns to the head tank 1 for recycling.
4) After reacting for a period of time, analyzing the oil phase in the head tank, ending the reaction if the content of the residual pinene is 5% -7%, collecting and processing the residual oil phase which is red oil, and supplementing acid liquor for reuse.
Specific examples are given below.
Example 1
Adding 500kg of pinene into a head tank 1, adding 1250kg of sulfuric acid solution with the concentration of 30 percent into a square tank 3, adding 0.5kg of peregal and 0.5kg of acetic acid into the sulfuric acid solution, starting a circulating pump 4, starting a lateral suction port to feed pinene, starting an air inlet pipeline x to control the flow to be 50m3And h, controlling the feeding amount of cooling water to ensure that the temperature of the materials in the square groove 3 is 30 ℃. When the oil phase overflows into the filter, the suction filtration is started, and the oil is pumped into the head tank.
And when the content of the oil phase pinene in the head tank is lower than 7%, the reaction is finished. And (4) carrying out centralized treatment on the red oil in the head tank, analyzing the acid value of the sulfuric acid solution in the square tank, and supplementing a proper amount of the sulfuric acid solution for next batch. The crystals were transferred to a centrifuge, spun and weighed.
490kg of hydroterpineol is obtained, and the material loss is 4 percent; the conversion was 93% and the selectivity was 75.2%.
Example 2
Adding 500kg of pinene into a head tank 1, adding 1250kg of sulfuric acid solution with the concentration of 25 percent into a square tank 3, adding 0.5kg of peregal and 0.5kg of acetic acid into the sulfuric acid solution, starting a circulating pump 4, starting a lateral suction port to feed pinene, starting an air inlet pipeline x to control the flow to be 50m3And h, controlling the feeding amount of cooling water to ensure that the temperature of the materials in the square groove 3 is 30 ℃. When the oil phase overflows into the filter, the suction filtration is started, and the oil is pumped into the head tank.
And when the content of the oil phase pinene in the head tank is lower than 5%, the reaction is finished. And (4) carrying out centralized treatment on the red oil in the head tank, analyzing the acid value of the sulfuric acid solution in the square tank, and supplementing a proper amount of the sulfuric acid solution for next batch. The crystals were transferred to a centrifuge, spun and weighed.
486kg of terpene hydrate glycol is obtained, and the material loss is 4.2 percent; the conversion was 92.3% and the selectivity was 75.23%.
Example 3
Adding 500kg of pinene into a head tank 1, adding 1250kg of sulfuric acid solution with the concentration of 30 percent into a square tank 3, adding 0.5kg of peregal and 0.5kg of acetic acid into the sulfuric acid solution, starting a circulating pump 4, starting a lateral suction port to feed pinene, starting an air inlet pipeline x to control the flow to be 50m3And h, controlling the feeding amount of cooling water to ensure that the temperature of the materials in the square groove 3 is 25 ℃. When the oil phase overflows into the filter, the suction filtration is started, and the oil is pumped into the head tank.
And when the content of the oil phase pinene in the head tank is lower than 6%, the reaction is finished. And (4) carrying out centralized treatment on the red oil in the head tank, analyzing the acid value of the sulfuric acid solution in the square tank, and supplementing a proper amount of the sulfuric acid solution for next batch. The crystals were transferred to a centrifuge, spun and weighed.
495kg of terpene hydrate glycol is obtained, and the material loss is 5.3 percent; conversion 93.3%, selectivity 76.62%
Firstly, mixing pinene and a sulfuric acid solution through a Venturi ejector for reaction, and cooling the inside of a container by using an inner coil pipe to form white crystals; the method comprises the following steps that (1) oil-water mixed liquid in a container enters a Venturi ejector after being pressurized by a pump to form jet flow, the side face sucks materials and air in a head tank, the two phases are vigorously mixed in the Venturi tube and then enter the container, the two phases in the container are cooled and then layered, an upper oil phase overflows and enters a filter, vacuum filtration is formed through the head tank, the oil phase enters the head tank, part of solid particles are left on filter cloth, and after multiple times of mixing, the reaction reaches the end point; in order to enhance the mixing of oil and water, a proper amount of surfactant peregal and acetic acid are added into the solution. And after the reaction is finished, cooling, allowing crystals floating on the water surface in the container to enter a filter for suction filtration, allowing the red oil to enter a head tank, and replenishing the residual acid liquor in the container for repeated use. As can be seen from the examples, the method has simple operation steps, the reaction result is similar to that of the traditional stirred tank, and the method can be applied to large-scale industrial production.
Claims (8)
1. A method of synthesizing hydroterpineol in a venturi jet device, characterized by comprising the steps of:
1) preparing a sulfuric acid solution in a square groove with a built-in cooling coil, and adding a quantitative emulsifier peregal and a regulator acetic acid solution;
2) quantitative pinene or turpentine is put into the head tank;
3) starting a pump to pump the acid solution in the square groove into the Venturi ejector and then into the square groove to form a loop;
4) opening a lateral feed inlet of the Venturi ejector, sucking pinene or turpentine materials in the high-level groove into the Venturi ejector, and supplementing 30-50 m3Air amount per hour;
5) starting a coil pipe, namely cooling water at 0 ℃, and controlling the flow rate to enable the temperature of the solution in the square groove to be 25-30 ℃;
6) after the oil-water two phases enter the square groove, the oil-water two phases are cooled and layered, and the upper oil phase enters the filter through an overflow port;
7) sampling an oil phase in the head tank, analyzing the content of pinene or turpentine, if the content of pinene is 5-7%, ending the reaction, stopping the pump, and stopping vacuum;
8) the crystal terpene glycol hydrate in the filter is used for the next reaction, and the sulfuric acid solution in the square groove is properly supplemented and recycled.
2. The method for synthesizing hydroterpineol in a venturi jet device according to claim 1, wherein in step 1), the percentage concentration of the sulfuric acid solution is 25% to 30%.
3. The method for synthesizing hydroterpineol in a venturi jet device according to claim 1, wherein in step 1), the mass ratio of peregal to pinene is (1-1.5): 1000.
4. The method for synthesizing hydroterpineol in a venturi jet device as claimed in claim 1, wherein in step 1), the mass ratio of acetic acid to pinene is (1-2): 1000.
5. The method for synthesizing hydroterpineol in a venturi jet device according to claim 1, wherein in step 2), the head tank is a raw material tank or a suction filtration solution receiving tank.
6. The method for synthesizing hydroterpineol in a venturi injection device as claimed in claim 1, wherein in step 2), the mass ratio of pinene or turpentine to sulfuric acid solution is 1: 2.5-3.
7. The method for synthesizing hydroterpineol in the Venturi injection device according to claim 1, wherein in the step 3), the flow rate of the pump is controlled to be 40-60 m3And h, adopting fluorine lining at the overflowing part of the pump.
8. The method for synthesizing hydroterpineol in a venturi jet device according to claim 1, wherein in step 6), if crystals are generated, the crystals enter a filter along with an oil phase, and the oil phase enters an elevated tank for recycling after suction filtration.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110374286.XA CN113200824A (en) | 2021-04-07 | 2021-04-07 | Method for synthesizing hydroterpineol in Venturi injection device |
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| CN202110374286.XA CN113200824A (en) | 2021-04-07 | 2021-04-07 | Method for synthesizing hydroterpineol in Venturi injection device |
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Citations (7)
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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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| CN210314059U (en) * | 2019-08-05 | 2020-04-14 | 江西赫信化学有限公司 | Dewatering device is used in production of high-purity terpineol |
| CN111320572A (en) * | 2020-04-15 | 2020-06-23 | 杭州瑞思新材料有限公司 | Preparation method of substituted pyridine |
| CN212524111U (en) * | 2020-02-18 | 2021-02-12 | 清华大学 | Reactor for continuously producing polycarbonate oligomer |
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2021
- 2021-04-07 CN CN202110374286.XA patent/CN113200824A/en active Pending
Patent Citations (7)
| 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 |
| CN102718632A (en) * | 2012-06-29 | 2012-10-10 | 厦门百度科技开发有限公司 | Method for preparing terpin hydrate by virtue of continuous hydration |
| CN204058305U (en) * | 2014-09-02 | 2014-12-31 | 江西威科油脂化学有限公司 | The industrialization synthesizer of primary fatty acids acid amides |
| CN108752163A (en) * | 2018-06-28 | 2018-11-06 | 广西壮族自治区林业科学研究院 | A kind of method turpentine oil synthesis terpinum and prepare terpinol, acetic acid esters |
| CN210314059U (en) * | 2019-08-05 | 2020-04-14 | 江西赫信化学有限公司 | Dewatering device is used in production of high-purity terpineol |
| CN212524111U (en) * | 2020-02-18 | 2021-02-12 | 清华大学 | Reactor for continuously producing polycarbonate oligomer |
| CN111320572A (en) * | 2020-04-15 | 2020-06-23 | 杭州瑞思新材料有限公司 | Preparation method of substituted pyridine |
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