CN1212316C - Method and apparatus for continuous production of pinan-hydroperoxide prepared by autoxidation of pinane - Google Patents
Method and apparatus for continuous production of pinan-hydroperoxide prepared by autoxidation of pinane Download PDFInfo
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- CN1212316C CN1212316C CN02148572.0A CN02148572A CN1212316C CN 1212316 C CN1212316 C CN 1212316C CN 02148572 A CN02148572 A CN 02148572A CN 1212316 C CN1212316 C CN 1212316C
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- Prior art keywords
- pinane
- tower
- oxidizing tower
- valve
- hydroperoxide
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- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 229930006728 pinane Natural products 0.000 title claims abstract description 75
- 238000010924 continuous production Methods 0.000 title claims abstract description 11
- 238000006701 autoxidation reaction Methods 0.000 title claims description 14
- 238000000034 method Methods 0.000 title abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims description 57
- 238000000926 separation method Methods 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract 7
- 239000000243 solution Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- LIZVXGBYTGTTTI-UHFFFAOYSA-N 2-[(4-methylphenyl)sulfonylamino]-2-phenylacetic acid Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C(O)=O)C1=CC=CC=C1 LIZVXGBYTGTTTI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 229930003427 Vitamin E Natural products 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for continuously preparing pinane radical hydroperoxide by pinane auto-oxidation. The present invention is characterized in that pinane solution composed of pinane and catalysts is preheated, and is filled in an oxidation tower from the top; preheated oxygen or preheated air or the gas mixture of the preheated oxygen and the preheated air is transmitted to the oxidation tower simultaneously; the transmitted gas thoroughly contacts and reacts with the pinane solution; pinane radical hydroperoxide is generated by partial reaction in order to obtain product solution composed of the generated pinane radical hydroperoxide and the pinane; partial product solution is heated or cooled, and is added in the oxidation tower together with the preheated pinane from the top of the oxidation tower for further reaction; the present invention controls the temperature of liquid added to the oxidation tower, the temperature of the transmitted gas, the flow capacity of the added pinane, the flow capacity of the product solution circularly added, and the flow capacity of the gas in order to regulate temperature and pressure in the oxidation tower until the content of the pinane radical hydroperoxide in the product solution meets requirements in such circulation; pinane radical hydroperoxide products are continuously released; the pinane and the product solution are continuously added to the oxidation tower simultaneously for continuous production. The present invention discloses a production apparatus of the method.
Description
One, technical field
The present invention relates to the production equipment of pinane base hydroperoxide.
Two, background technology
Pinane base hydroperoxide are intermediates of making phantol (spices) and vitamin-E etc., can be got by the pinane autoxidation, and its reaction equation is as follows:
Pinane pinane base hydroperoxide
At present the typical process for preparing pinane base hydroperoxide by the pinane autoxidation as shown in Figure 1.
A certain amount of pinane and catalyzer are added batch still, under agitation continuous aerating oxygen or air.Timing sampling is analyzed the autoxidation degree of pinane in the reaction process, gets final product discharging after reaching specified requirement.The nucleus equipment of this process using is a stirred-tank reactor, is characterized in periodical operation, and processing condition are wayward, unstable product quality, and the throughput of equipment is less.
Three, summary of the invention
The objective of the invention is shortcoming, a kind of continuous production method and device thereof that is prepared pinane base hydroperoxide by the pinane autoxidation is provided at present pinane automatic oxidation reaction batch production pinane base hydroperoxide process.
Technical scheme of the present invention is as follows:
A kind of pinane autoxidation prepares the continuous production method of pinane base hydroperoxide, it is to join the oxidizing tower from the top after the pinane solution preheating that pinane and catalyzer are formed, feed oxygen or air simultaneously through preheating, perhaps both gas mixtures, the gas of feeding is contacted fully with pinane solution, make it reaction, partial reaction becomes pinane base hydroperoxide, the resultant solution that pinane base hydroperoxide that obtain generating and pinane are formed, getting the pinane of part resultant solution after heating or cooling back and preheating more together joins the oxidizing tower from the oxidizing tower top, make it further reaction, so circulation, the temperature that adds the liquid and the feeding gas of oxidizing tower by control, and control adds the flow and the gas flow of the resultant solution of pinane and circulation adding, regulate the temperature and pressure in the oxidizing tower, after the content of the pinane base hydroperoxide of resultant solution reaches requirement, constantly emit product pinane base hydroperoxide, constantly pinane and resultant solution are joined in the oxidizing tower simultaneously, form continuous production.
In the above-mentioned production method, the temperature in the oxidizing tower is controlled at 70～100 ℃.
In the above-mentioned production method, catalyzer is the free radical reaction initiator, as azobenzoic acid.
The adding of catalyzer is disposable in the above-mentioned production method, after reaction has begun, no longer needs to add catalyzer, only needs pinane and resultant solution constantly are added in the oxidizing tower.
In the above-mentioned production method, be that 50～80% the pinanes after heating or cooling back and preheating of getting the resultant solution discharge together join in the oxidizing tower.
Above-mentioned pinane autoxidation prepares the production equipment of the continuous production method of pinane base hydroperoxide, it comprises mixing tank, charge pump, liquor preheater, gas preheater, oxidizing tower, overhead condenser, heat exchange basin at the bottom of the tower, recycle pump and under meter, pressure transmitter, temperature sensor, pinane is connected mixing tank through pipeline with valve respectively with catalyzer raw material basin, mixing tank is connected with charge pump, charge pump links to each other with liquor preheater with under meter by valve, the outlet of liquor preheater communicates with the top of oxidizing tower, the air or oxygen transfer lime links to each other with gas preheater through under meter, the outlet of gas preheater communicates with the bottom of oxidizing tower, the top of oxidizing tower has pipeline to link to each other with overhead condenser, overhead condenser has pipeline that phlegma is back to the oxidizing tower top, the products export valve is arranged at the bottom of oxidizing tower, and there is pipeline to communicate with heat exchange basin at the bottom of the tower, the heat exchange basin has heat-exchanger rig at the bottom of the tower, can feed heating medium or heat-eliminating medium heats or cools off, the heat exchange tank bottom has pipeline to link to each other with the oxidizing tower top with under meter through recycle pump at the bottom of the tower, the heat exchange basin has products export at the bottom of the tower, is provided with temperature sensor and pressure transmitter in the oxidizing tower.
In the above-mentioned production equipment, oxidizing tower is a cylindrical-shaped tower, and its internal structure is the structure of board-like separation column, and column plate can be sieve plate, bubble cap plate, valve tray, tongue type column plate, inclined hole sieve plate or guide float valve tray etc.The quantity of column plate can be 4～60, with 10～40 be the best, in the bottom of oxidizing tower gas introduction tube and valve are arranged.The top of oxidizing tower is provided with venting port, and has pipeline to link to each other with overhead condenser, and overhead condenser has blow-down pipe.It is to guarantee that oxygen contacts fully, reacts with pinane that oxidizing tower adopts the structure of separation column.Oxidizing tower can be provided with gas introduction tube and valve at the different heights of body of the tower, can be in the different heights control air input of body of the tower, to guarantee that W-response is good in the oxidizing tower.Different heights in the oxidizing tower can be provided with temperature sensor, and bottom and top are provided with pressure transmitter.
In the above-mentioned production equipment, mixing tank is the stirred pot that metal or non-metallic material are made, and its effect makes pinane and catalyst mix even when being the equipment entry into service.
In the above-mentioned production equipment, charge pump can be liquid transporting apparatus such as impeller pump, propeller pump, toothed gear pump, reciprocation pump, is best with the impeller pump.The transfusion ability of charge pump can be determined according to the size of throughput.Reinforced pump outlet can have a branch road to link to each other with mixing tank with valve, so that control pinane solution enters the flow of oxidizing tower.
In the above-mentioned production equipment, liquor preheater can be telescoping, shell and tube or recuperative heat exchanger such as board-like.The heat interchanging area of interchanger can be determined according to heat balance.When heat interchanging area hour, be advisable with double-pipe exchanger, when heat interchanging area is big, be advisable with shell and tube heat exchanger.Heating medium can be hot water or steam, with hot water for well.
In the above-mentioned production equipment, gas preheater can be recuperative heat exchangers such as telescoping, shell and tube, board-like or plate-fin, is best with the plate-fin heat exchanger, and the heat interchanging area of interchanger can be determined according to heat balance.
In the above-mentioned production equipment, overhead condenser is tubular type or the board-like recuperative heat exchanger that metal or non-metallic material are made, and is used for reclaiming the organism that oxidizing tower is discharged gas.
In the above-mentioned production equipment, recycle pump can be liquid transporting apparatus such as impeller pump, propeller pump, toothed gear pump, reciprocation pump, is best with the impeller pump.The transfusion ability of recycle pump can determine that outlet of circulating pump can link to each other with heat exchange basin at the bottom of the tower with valve through an arm according to the size of liquid circulation amount, so that the circulation of control resultant solution joins the flow in the oxidizing tower.
Adopt pinane autoxidation of the present invention to prepare the continuous production method and the production equipment of pinane base hydroperoxide, can be easily the production method of pinane base hydroperoxide be improved to continuous production by the intermittent type in past, quality product improves, steady quality, facility investment is little, output is big, and energy consumption is low.
Four, description of drawings
Fig. 1 prepares the existing typical process synoptic diagram of pinane base hydroperoxide for the pinane autoxidation, and wherein 1 is still or reactor; 2 is condenser; The A pinane; The B catalyzer; C oxygen; D steam; The E water coolant; The F chilled brine.
Fig. 2 is the continuous production processes synoptic diagram that pinane of the present invention prepares pinane base hydroperoxide, and wherein 3 is mixing tank; 4,5,7,10,11,16,17,18,19,21,22,24,26,27,30,31,32,33 is valve; 6 is charge pump; 8,12,13,15 is under meter; 9 is liquor preheater; 14 is gas preheater; 20 is oxidizing tower; 23 is overhead condenser; 25 is the phegma basin; The F chilled brine; The G air; The H heating medium; The I heat-eliminating medium; The J product; The K thief hole; The P pressure transmitter; The T temperature sensor.
Five, embodiment
Embodiment 1: prepare pinane base hydroperoxide by the pinane autoxidation.Adopt apparatus of the present invention, as shown in Figure 2, it mainly comprises heat exchange basin 28 at the bottom of mixing tank 3, charge pump 6, liquor preheater 9, gas preheater 14, oxidizing tower 20, overhead condenser 23, phegma basin 25, the tower, recycle pump 29 and under meter, pipeline and valve, as shown in Figure 2.The internal diameter of oxidizing tower 20 is 500mm, in adorn 20 sieve plates.The pinane inlet amount is 600Kg/h, the disposable adding 1.5Kg of catalyzer (radical initiator) azobenzoic acid, 600Kg pinane and catalyzer join mixing tank 3 through pipeline, be stirred after valve 4, charge pump 6, valve 7 and under meter 8 enter liquor preheater 9 is preheated to 70 ℃ and adds from oxidizing tower 20 cats head, the heating medium H of liquor preheater 9 is a hot water, oxygen C enters gas preheater 14 through valve 10 and under meter 12 simultaneously, and the amount of aerating oxygen is 47.6m
3/ h (normal conditions), gas are preheating to 70 ℃ and enter oxidizing tower 20 by at the bottom of oxidizing tower 20 towers or middle part, and the gas inlet of several inlet mouths is regulated according to sectional temperature in the oxidizing tower 20, and true pressure is controlled at 1～1.2Kg/cm in the tower
2, temperature is controlled at 70～100 ℃ in the tower.Oxidizing tower 20 cat head gases are through condenser 23 condensations, and phlegma turns back in the oxidizing tower 20 from oxidizing tower 20 tops through phegma basin 25, and incondensable gas is through valve 24 emptying, and overhead condenser 23 usefulness chilled brines are made refrigerant, play circulation.Pinane contacts with oxygen in oxidizing tower 20, automatic oxidation reaction takes place, part generates pinane base hydroperoxide, resultant solution flows out from the oxidizing tower bottom, heat exchange basin 28 at the bottom of valve 27 enters tower, resultant solution is through heat exchange basin at the bottom of the tower 28 heating or be cooled to 70 ℃ and pump in the tower from oxidizing tower 20 cats head through recycle pump 29, valve 33 and under meter, reacts again.Pump flow is 2828Kg/h, resultant solution can be at the bottom of arm and valve 32 return tower heat exchange basin 28 so that control pumps into the flow in the oxidizing tower 20.Internal circulating load is controlled at 50～80% of resultant solution flow, concentration according to oxidizing tower bottom sampling analysis pinane base hydroperoxide is decided, the low internal circulating load of concentration increases, the high internal circulating load of concentration reduces, pinane base hydroperoxide concentration reach about 39% (Wt) fixed product concentration, then system reaches the continous-stable running status, drive to be about 3.6h to continous-stable running status required time, this moment, discharging flow was 648Kg/h, and wherein the concentration of pinane base hydroperoxide is about 39.8% (Wt).
Embodiment 2: prepare pinane base hydroperoxide by the pinane autoxidation.
Adopt apparatus of the present invention shown in Figure 2, flow process, step and condition are with embodiment 1, but the column plate in the oxidizing tower 20 changes 20 blocks of valve traies into.The inlet amount pinane is 800Kg/h, and add-on of catalyzer is 2.0Kg, and oxygen feeding amount is 32m
3/ h (mark condition), the while bubbling air, air feeding amount is 150m
3/ h (mark condition), pump flow is 2828Kg/h, and it is 7.8h that system reaches continous-stable running status required time, and discharging flow is 864Kg/h, and wherein the concentration of pinane hydroperoxide is about 39.9% (Wt).
Embodiment 3: prepare pinane base hydroperoxide by the pinane autoxidation.
Adopt apparatus of the present invention shown in Figure 2, flow process, step and condition are with embodiment 2, but the column plate in the oxidizing tower 20 changes 20 guide float valve trays into.The inlet amount pinane is 800Kg/h, the disposable adding 2Kg of catalyzer, and oxygen feeding amount is 32m
3/ h (mark condition), air feeding amount is 150m
3/ h (mark condition), pump flow is 2828Kg/h, and it is 7.6h that system reaches continous-stable running status required time, and discharging flow is 865Kg/h, and wherein the concentration of pinane hydroperoxide is about 40.1% (Wt).
Claims (6)
1. a pinane autoxidation prepares the continuous production device of pinane base hydroperoxide, it is characterized in that comprising mixing tank (3), charge pump (6), liquor preheater (9), gas preheater (14), oxidizing tower (20), overhead condenser (23), heat exchange basin (28) at the bottom of the tower, recycle pump (29) and under meter, pressure transmitter (P), temperature sensor (T), pinane is connected mixing tank (3) through pipeline respectively with catalyzer raw material basin with valve, mixing tank (3) is connected with charge pump (6), charge pump (6) links to each other with liquor preheater (9) with under meter (8) by valve (7), the outlet of liquor preheater communicates with the top of oxidizing tower (20), the air or oxygen transfer lime is through under meter (12,13) link to each other with gas preheater (14), the outlet of gas preheater (14) communicates with the bottom of oxidizing tower (20), the top of oxidizing tower (20) has pipeline to link to each other with overhead condenser (23), the pipeline of overhead condenser is back to oxidizing tower (20) top with phlegma, products export valve (22) is arranged at the bottom of oxidizing tower (20), oxidizing tower (20) bottom has pipeline to communicate with heat exchange basin (28) at the bottom of the tower, heat exchange basin (28) has heat-exchanger rig at the bottom of the tower, heat exchange basin (28) bottom has pipeline to link to each other with oxidizing tower (20) top with under meter (33) through recycle pump (29) at the bottom of the tower, heat exchange basin (28) has products export at the bottom of the tower, is provided with temperature sensor (T) and pressure transmitter (P) in the oxidizing tower (20).
2. production equipment according to claim 1, the internal structure that it is characterized in that described oxidizing tower (20) is the structure of board-like separation column, and gas introduction tube and valve (16) are arranged in the bottom of oxidizing tower (20).
3. production equipment according to claim 1 is characterized in that oxidizing tower (20) is provided with gas introduction tube and valve (16,17,18,19) at the different heights of body of the tower.
4. production equipment according to claim 3 is characterized in that the different heights in the oxidizing tower (20) is provided with temperature sensor (T), and bottom and top are provided with pressure transmitter (P).
5. production equipment according to claim 1 is characterized in that the outlet of described charge pump (6) has an arm to link to each other with mixing tank (3) with valve (5).
6. production equipment according to claim 1 is characterized in that the outlet of described recycle pump (29) has an arm and valve (32) to link to each other with heat exchange basin (28) at the bottom of the tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02148572.0A CN1212316C (en) | 2002-12-18 | 2002-12-18 | Method and apparatus for continuous production of pinan-hydroperoxide prepared by autoxidation of pinane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02148572.0A CN1212316C (en) | 2002-12-18 | 2002-12-18 | Method and apparatus for continuous production of pinan-hydroperoxide prepared by autoxidation of pinane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1422845A CN1422845A (en) | 2003-06-11 |
| CN1212316C true CN1212316C (en) | 2005-07-27 |
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| CN02148572.0A Expired - Fee Related CN1212316C (en) | 2002-12-18 | 2002-12-18 | Method and apparatus for continuous production of pinan-hydroperoxide prepared by autoxidation of pinane |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102911102B (en) * | 2012-10-26 | 2014-06-25 | 崇左森隆林化科技有限公司 | Method and device for producing pinane hydrogen peroxide |
| CN104151224A (en) * | 2014-08-13 | 2014-11-19 | 广西梧松林化集团有限公司 | Method for synthesizing pinane superoxide by oxidizing pinane |
| CN111054296A (en) * | 2019-12-02 | 2020-04-24 | 河南金鹏化工有限公司 | Continuous production device and process for thiodicarb salinization reaction |
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