CN111662171B - Method for removing cyclohexanone and intermediate components in cyclohexanol - Google Patents
Method for removing cyclohexanone and intermediate components in cyclohexanol Download PDFInfo
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- CN111662171B CN111662171B CN201910166490.5A CN201910166490A CN111662171B CN 111662171 B CN111662171 B CN 111662171B CN 201910166490 A CN201910166490 A CN 201910166490A CN 111662171 B CN111662171 B CN 111662171B
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 240
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 238000000034 method Methods 0.000 title claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 127
- 239000007788 liquid Substances 0.000 claims abstract description 80
- 150000002576 ketones Chemical class 0.000 claims abstract description 21
- -1 alcohol ketone Chemical class 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 40
- 238000010992 reflux Methods 0.000 claims description 20
- 230000006837 decompression Effects 0.000 claims description 11
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 50
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 description 19
- 239000012535 impurity Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 238000005192 partition Methods 0.000 description 11
- 239000000945 filler Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 7
- 239000002699 waste material Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910009378 Zn Ca Inorganic materials 0.000 description 4
- GKRALBJDXHXFNB-UHFFFAOYSA-N butoxycyclohexane Chemical compound CCCCOC1CCCCC1 GKRALBJDXHXFNB-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
-
- 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
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for removing cyclohexanone and intermediate components in cyclohexanol, which comprises the following steps: 1) Rectifying ketone tower bottom liquid in a crude alcohol tower with a side line, returning crude alcohol tower top distillate to the crude alcohol ketone tank, feeding the side line extraction liquid into the crude alcohol tank, and discharging crude alcohol tower bottom liquid; 2) Leading out crude alcohol from the crude alcohol tank to a vacuum tower for vacuum rectification, enabling distillate at the top of the vacuum tower to enter an atmospheric tower, and enabling kettle liquid of the vacuum tower to return to the crude alcohol tank; 3) And (3) carrying out normal-pressure rectification separation on the distillate at the top of the vacuum tower in an atmospheric tower, returning the distillate at the top of the atmospheric tower to the crude alcohol tank, and discharging the liquid at the bottom of the atmospheric tower. The method has the advantages that the content of cyclohexanone in the crude alcohol is greatly reduced after the treatment, meanwhile, the content of intermediate components can be maintained in a lower range, the cyclohexanol dehydrogenation conversion rate is greatly improved, the cyclohexanol dehydrogenation selectivity is improved, and the treatment capacity of a cyclohexanol dehydrogenation device is improved.
Description
Technical Field
The invention relates to a method for removing cyclohexanone and intermediate components in cyclohexanol, belonging to the field of cyclohexanone preparation.
Background
Cyclohexanone is prepared by oxidation of cyclohexane, typically by the steps of:
(1) Oxidizing cyclohexane by using a gas containing molecular oxygen to generate a cyclohexane oxidation solution containing substances such as cyclohexyl hydroperoxide, cyclohexanol, cyclohexanone and the like;
(2) Treating the cyclohexane oxidation solution with an alkaline solution to decompose the cyclohexyl hydroperoxide therein to form cyclohexyl alcohol and cyclohexanone, and neutralizing the acid in the oxidation solution to saponify the ester;
(3) Recycling unreacted cyclohexane by distillation, and feeding the rectifying still liquid without cyclohexane and cyclohexanol dehydrogenation product into a crude alcohol ketone tank;
(4) Materials led out from the crude alcohol ketone tank enter a light tower for vacuum rectification, components which are more volatile than cyclohexanone are separated from the top of the tower, and cyclohexanone, cyclohexanol and components which are more difficult to volatilize than cyclohexanone are discharged from the tower kettle;
(5) Feeding the materials in the light tower kettle into a ketone tower for vacuum rectification, obtaining cyclohexanone product from the tower top, and discharging cyclohexanol and components which are harder to volatilize than cyclohexanone from the tower kettle;
(6) The ketone tower bottom liquid enters an alcohol tower for vacuum rectification, components which are more volatile than cyclohexanol are distilled out from the top of the tower together with cyclohexanol, and are sent to a crude alcohol tank, and components which are more difficult to volatilize than cyclohexanol are discharged from the tower bottom;
(7) And (3) leading out materials from the crude alcohol tank to a cyclohexanol dehydrogenation process, wherein part of cyclohexanol is dehydrogenated into cyclohexanone, and the dehydrogenation product is led into the crude alcohol ketone tank and is used as a raw material of the light tower together with alkane tower kettle liquid.
From the above typical processes for cyclohexanone production, it can be seen that substances generated from cyclohexane oxidation and cyclohexanol dehydrogenation, which are volatile between cyclohexanone and cyclohexanol under the operating conditions of each rectification column, cannot be removed from the rectification process, and gradually accumulate in the rectification system, which have an influence on cyclohexanone production, and these substances are collectively called intermediate components.
These volatilities are mostly impurities with boiling point higher than cyclohexanol at normal pressure in the intermediate components between cyclohexanone and cyclohexanol, and because they are azeotroped with cyclohexanol under alcohol column rectification conditions, they distill overhead with cyclohexanol, resulting in a gradual increase in the content of intermediate components in the crude alcohol tank material, often exceeding 10% in total. The existing method is that when the device is overhauled or stopped, the components with higher content of the intermediate components in the crude alcohol ketone tank and the crude alcohol tank are treated as waste materials, and after normal driving, the content of the intermediate components in the rectification materials is gradually increased. These higher levels of intermediate components can adversely affect the production of cyclohexanone: firstly, the substances are evaporated in an alcohol tower, energy is consumed, then the substances enter a cyclohexanol dehydrogenation process along with cyclohexanol, and the substances return to a crude alcohol ketone tank after evaporation, temperature rise, reaction and temperature reduction, and enter a light tower, a ketone tower and an alcohol tower again, so that the invalid circulation of the substances is caused, the energy consumption is increased, and the equipment space is occupied; secondly, when the content of the impurities is high, a small amount of the impurities enters a cyclohexanone product at the top of the ketone tower, so that the quality of the cyclohexanone is reduced; thirdly, in order to ensure the quality of cyclohexanone, the content of cyclohexanone in the material in the ketone tower kettle has to be improved, so that excessive cyclohexanone is brought into the raw material for dehydrogenating cyclohexanol, the conversion rate of cyclohexanol in the dehydrogenation process is reduced, the condensation side reaction of cyclohexanone is increased, and the selectivity of cyclohexanol dehydrogenation is reduced; fourthly, the crude alcohol ketone material and the crude alcohol material with higher content of intermediate components are treated as waste materials during the stopping period, so that the material consumption of cyclohexanone production is increased.
The production amount of the intermediate components is small, for example, a 10 ten thousand ton/year cyclohexanone device is taken as an example, the production amount of the intermediate components is about 40 tons/year, and the production amount of the intermediate components is 5kg/h, so that the concentration of the intermediate components in the rectification system can be kept constant only by removing the intermediate components at the speed of 5kg/h.
Wu Shouhui in petrochemical 1983,12 (10): 642-649 it is pointed out that impurities contained in cyclohexanol can increase the thermal instability of cyclohexanol itself, with an increase of 3-4% in high boiling substances when 90-91% of cyclohexanol by industrial rectification is passed through a superheater, and with 98-98.8% of cyclohexanol, almost unchanged. The dehydrogenation selectivity is reduced by about 4% when industrially rectified cyclohexanol is used, compared with that when pure cyclohexanol is used, so that the cyclohexanol dehydrogenation raw material should be refined to reduce the impurity content in cyclohexanol as much as possible, for example, a cutting tower is added in an alcohol ketone rectification system, but no specific method is given therein.
Chinese patent 201620707871.1 discloses a device for removing impurity butyl cyclohexyl ether in the production process of cyclohexanone, which is characterized in that a rectifying tower is added behind a cyclohexanol evaporator to carry out normal pressure or pressurized rectification on crude cyclohexanol, and part of butyl cyclohexyl ether is discharged from a tower kettle to a heavy component tank, so that the aim of reducing the content of intermediate components in the crude cyclohexanol is fulfilled. But the content of butyl cyclohexyl ether in the discharged tower kettle liquid is only 25-35%, and the rest components are cyclohexanol, which means that 2-3 times of cyclohexanol with butyl cyclohexyl ether is treated as a byproduct, thereby increasing material consumption. In addition, the problem of too high cyclohexanone content in the crude cyclohexanol still remains.
Chinese patent 201610837394.5 discloses a process for preparing cyclohexanone by dehydrogenating cyclohexanol, wherein the equipment of the cyclohexanol dehydrogenation procedure consists of a cyclohexanol evaporator, a vapor-liquid separator, a normal pressure or pressurized rectifying tower and a cyclohexanol dehydrogenation reactor; the rectifying tower is only provided with a stripping section, and the tower kettle is provided with a reboiler. The technology can greatly reduce the concentration of the methylcyclohexanone, the heptanone and the analogues thereof contained in the materials of the cyclohexanone rectification process and the cyclohexanol dehydrogenation process, and reduce the circulation and accumulation of the methylcyclohexanone, the heptanone and the analogues thereof in the cyclohexanone rectification process and the cyclohexanol dehydrogenation process. However, the process can not reduce the content of cyclohexanone in the cyclohexanol raw material, and the material discharged from the tower still contains about 30% of cyclohexanol, so that the material consumption is increased. In addition, these impurities, which are very low in content, are removed from the column bottom under normal pressure or pressurized conditions, requiring high energy consumption.
One common feature of these patents is that these intermediate components are removed from the bottoms by means of only atmospheric or pressurized rectification, and when the amount of these intermediate components in the feed is not high, more energy is required to remove these impurities from the bottoms, for example, when a feed containing 90% cyclohexanol and 10% intermediate components is subjected to atmospheric or pressurized rectification, a reflux ratio of 4 is set, and at least 45 parts of cyclohexanol is required to be evaporated per 1 part of intermediate component removed; if the reflux ratio is set to 4 when the material containing 96% of cyclohexanol and 4% of intermediate components is rectified under normal pressure or under pressure, at least 120 parts of cyclohexanol is evaporated per 1 part of intermediate component removed, and the energy consumption is increased sharply.
At the same time, cyclohexanol dehydrogenation is an endothermic equilibrium reaction, and increasing the concentration of cyclohexanone in the raw material shifts the equilibrium toward the raw material, and reduces the yield of cyclohexanol dehydrogenation, so that the concentration of cyclohexanone in the raw material should be reduced as much as possible. The cyclohexanone concentration in the ketone tower kettle material is often controlled to be more than 4 percent, sometimes up to 8 percent and even up to 10 percent, so that the cyclohexanone in the ketone tower kettle material is also necessary to be separated, and the quality of the cyclohexanone in the ketone tower top product is ensured by the limitation of the separation capability of the intermediate product and the ketone tower.
Disclosure of Invention
Aiming at the problem that the dehydrogenation productivity of cyclohexanol is lower due to the fact that the content of cyclohexanone and intermediate components in crude cyclohexanol is too high in the existing industrial production device, the invention aims to provide a method for removing cyclohexanone and intermediate components in cyclohexanol.
In order to achieve the above object, the present invention provides a method for removing cyclohexanone and intermediate components in cyclohexanol, comprising the steps of:
1) Rectifying ketone tower bottom liquid in a crude alcohol tower with a side line, returning crude alcohol tower top distillate to the crude alcohol ketone tank, feeding the side line extraction liquid into the crude alcohol tank, and discharging crude alcohol tower bottom liquid X oil;
2) Leading out crude alcohol from the crude alcohol tank to a vacuum tower for vacuum rectification, enabling distillate at the top of the vacuum tower to enter an atmospheric tower, and enabling kettle liquid of the vacuum tower to return to the crude alcohol tank;
3) And (3) carrying out normal-pressure rectification separation on the distillate at the top of the vacuum tower in an atmospheric tower, returning the distillate at the top of the atmospheric tower to the crude alcohol tank, and discharging the liquid at the bottom of the atmospheric tower.
Preferably, in the step 1), the crude alcohol column is a baffle rectifying column. The baffle is located crude alcohol tower middle part, lays perpendicularly, separates the crude alcohol tower into four regions, and baffle upper portion is public rectification section, and the baffle left side is the feed zone, and the baffle right side is the side and draws the section, and the baffle lower part is public stripping section.
The invention preferably adopts the baffle rectifying tower, so that equipment investment and energy consumption are saved, and meanwhile, tower top distillate, side line extract and tower bottom liquid can be better separated, thereby better achieving the aim of impurity removal and purification.
Preferably, in the step 1), the top pressure of the crude alcohol column is 1 to 10kPa, preferably 2 to 4kPa; the reflux ratio is 10 to 100, preferably 30 to 60.
More preferably, cyclohexanone is the main material in the distillate at the top of the crude alcohol tower, and the total content of cyclohexanol and intermediate components is not higher than 3wt%; the side-stream extraction liquid is mainly cyclohexanol, and the total content of cyclohexanone and X oil is not higher than 2wt%; the crude alcohol tower bottom liquid is mainly X oil, and the total content of cyclohexanone and cyclohexanol is not higher than 2wt%.
Preferably, in the step 2), the amount of the crude alcohol discharged from the crude alcohol tank to the pressure reduction column is 1 to 10% by weight, preferably 1 to 5% by weight, of the amount of the liquid discharged from the side stream of the crude alcohol column.
Preferably, in the step 2), the pressure at the top of the pressure reducing tower is 1 to 10kPa, preferably 1 to 5kPa; the reflux ratio is 5-20, preferably 10-15; the temperature of the tower top is 40-100 ℃, preferably 40-60 ℃; the temperature of the tower kettle is 60-120 ℃, preferably 60-100 ℃.
More preferably, the total content of the intermediate components in the top distillate of the vacuum column is not less than 20% by weight, and the total content of the intermediate components in the bottom liquid of the vacuum column is not more than 3% by weight.
Preferably, in the step 3), the pressure at the top of the atmospheric tower is normal pressure, and the reflux ratio is 5-20, preferably 10-15; the temperature of the tower top is 150-165 ℃, preferably 155-162 ℃; the temperature of the tower kettle is 200-220 ℃, preferably 205-215 ℃.
More preferably, the total content of intermediate components in the overhead distillate of the atmospheric tower is not more than 3% by weight, and the content of cyclohexanol in the bottom liquid of the atmospheric tower is not more than 3% by weight.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) According to the technical scheme of the invention, the content of cyclohexanone in the crude alcohol can be greatly reduced to below 1wt%, and the condensation side reaction speed caused by cyclohexanone in the heating process of the dehydrogenation raw material is greatly reduced.
2) According to the technical scheme of the invention, the content of the intermediate component in the crude alcohol can be gradually reduced, and finally the content is maintained in a lower content range, so that the material composition in the rectification process and the cyclohexanol dehydrogenation process tends to be stable, and the stable operation of the device is facilitated.
3) According to the technical scheme of the invention, the content of cyclohexanone in the crude alcohol is greatly reduced, meanwhile, the content of intermediate components can be maintained in a lower range, the content of cyclohexanol in a cyclohexanol dehydrogenation raw material is higher, the cyclohexanol dehydrogenation conversion rate is greatly improved, the treatment capacity of a cyclohexanol dehydrogenation device is increased, and the selectivity of cyclohexanol dehydrogenation is improved.
4) According to the technical scheme of the invention, the content of cyclohexanone and intermediate components in the crude alcohol is low, so that ineffective evaporation and heat loss thereof in the heating and cooling processes are reduced, and the energy consumption is reduced.
5) According to the technical scheme of the invention, by utilizing the characteristic that the intermediate component and cyclohexanol are azeotroped in a certain vacuum range, the intermediate component is concentrated to more than 20wt% by decompression and then rectified at normal pressure, compared with the normal pressure or pressurized rectification of crude cyclohexanol solution, the method has the advantages that a large amount of cyclohexanol is not required to be evaporated, the treatment capacity of an atmospheric tower is greatly reduced, the energy consumption is greatly reduced, the content of cyclohexanol in high-boiling-point impurities discharged from the kettle of the atmospheric tower is also greatly reduced, the material consumption is also reduced, and particularly, when the content of the intermediate component in dehydrogenation raw materials is lower, the energy consumption of the method can be greatly reduced.
Drawings
FIG. 1 is a schematic illustration of a process flow of the present invention;
wherein: 1. the method comprises the steps of crude alcohol tower, 11, ketone tower bottom liquid, 12, crude alcohol tower top distillate, 13, side line liquid, 14, crude alcohol tower bottom liquid, 2, crude alcohol tank, 21, material for cyclohexanol dehydrogenation step, 22, crude alcohol material for vacuum tower removal, 3, vacuum tower, 31, vacuum tower top distillate, 32, vacuum tower bottom liquid, 4, normal pressure tower, 41, normal pressure tower top distillate, 42 and normal pressure tower bottom liquid.
Detailed Description
The following examples are intended to further illustrate the present invention in conjunction with the drawings of the specification, and are not intended to limit the scope of the claims of the present invention.
In the embodiment of the invention, the diameter of a crude alcohol tower 1 is 3.6m, 250Y packing is filled in the crude alcohol tower, a partition plate or no partition plate is arranged in the crude alcohol tower, when the partition plate is arranged, the whole alcohol tower is divided into 4 areas, the upper part of the partition plate is a public rectifying section, the height of the packing is 12m, the left side of the partition plate is a feeding section, the upper part and the lower part of the partition plate are respectively filled with 6m, the right side of the partition plate is a side line extraction section, the upper part and the lower part of the partition plate are respectively filled with 6m, the lower part of the partition plate is a public stripping section, the height of the packing is 12m, and a liquid collector is arranged between every two sections of packing for liquid redistribution or side line discharge. The diameter of the vacuum tower 3 is 1.0m, 250Y filler is filled in the tower, the total height of the filler is 32m, the tower is divided into an upper section and a lower section, the heights of the filler are 18m and 14m in sequence, and the feeding is positioned between the two sections of filler. The diameter of the atmospheric tower 4 is 0.3m, 250Y filler is filled in the tower, the total height of the filler is 24m, the filler is divided into an upper section and a lower section, the heights of the filler are 10m and 14m in sequence, and the feeding is positioned between the two sections of filler.
The percentages in the following embodiments are by mass unless otherwise specified.
Example 1
The crude alcohol column of this example does not provide a partition:
the ketone tower bottom liquid is continuously fed into a crude alcohol tower at the speed of 12500kg/h, the ketone tower bottom liquid contains 87.61% of cyclohexanol, 3.96% of cyclohexanone, 4.44% of intermediate components and 3.99% of X oil, the tower top pressure is 3-4 kPa, the reflux ratio is 45, the crude alcohol tower top distillate is continuously discharged at the speed of 420kg/h, the side line extraction liquid is continuously discharged into a crude alcohol tank at the speed of 11580kg/h, and the crude alcohol tower bottom liquid is continuously discharged at the speed of 500 kg/h. The top temperature is 45-55 ℃, the side line discharge temperature is 70-80 ℃, the kettle temperature is 110-160 ℃, the top distillate contains 98.01% of cyclohexanone, 1.30% of cyclohexanol, the intermediate component is 0.69%, the side line discharge liquid contains 0.72% of cyclohexanone, 94.51% of cyclohexanol, the intermediate component is 4.77%, and the kettle liquid contains 0.25% of cyclohexanol and 99.75% of X oil.
The crude alcohol material from the decompression tower contains 94.51% of cyclohexanol, 0.72% of cyclohexanone and 4.77% of intermediate component, and is fed into the decompression tower at the speed of 192.3kg/h, the pressure at the top of the tower is 3-4 kPa, the reflux ratio is 15, the distillate at the top of the decompression tower is continuously discharged at the speed of about 17.3kg/h, and the liquid at the bottom of the decompression tower is continuously discharged at the speed of about 175 kg/h. The top temperature is 45-55 ℃, the kettle temperature is 85-100 ℃, the top distillate of the vacuum tower contains 62.05 percent of cyclohexanol, 7.90 percent of cyclohexanone, 30.05 percent of intermediate component, and the kettle liquid of the vacuum tower contains 97.72 percent of cyclohexanol, 0.01 percent of cyclohexanone and 2.27 percent of intermediate component. The feed to the pressure reduction column corresponds to 1.66% of the crude alcohol column side offtake.
The tower top distillate of the vacuum tower is pumped to an atmospheric tower, the flow rate is 17.3kg/h, the reflux ratio is 10, the tower top distillate of the atmospheric tower is continuously discharged at a speed of about 12.3kg/h, and the tower bottom liquid of the atmospheric tower is continuously discharged at a speed of about 5kg/h. The top temperature is 155-165 ℃, the kettle temperature is 200-220 ℃, the top distillate of the atmospheric tower contains 86.81 percent of cyclohexanol, 11.11 percent of cyclohexanone, 2.08 percent of intermediate component, and the kettle liquid of the atmospheric tower contains 1.08 percent of cyclohexanol and 98.92 percent of intermediate component. The feed to the atmospheric tower was equivalent to 0.15% of the crude alcohol column side offtake.
The crude alcohol composition before the method of this example was not employed was: cyclohexanol 80.40%, cyclohexanone 5.74%, impurity 13.86%; the process of this example was used and run to a composition stabilized cyclohexanol dehydrogenation feed composition of: 94.51% of cyclohexanol, 0.72% of cyclohexanone and 4.77% of intermediate component. The cyclohexanone removal rate was 87.5%, and the steam consumption required for cyclohexanone removal and cyclohexanol distillation was about 0.40t steam/t. The removal rate of the intermediate component is 65.6%, and the steam consumption required for the intermediate component removal is about 20.6t steam/t intermediate component.
Example 2
The crude alcohol column of this embodiment is provided with a partition plate:
the ketone tower bottom liquid is continuously fed into a crude alcohol tower at the speed of 12500kg/h, the ketone tower bottom liquid contains 87.61% of cyclohexanol, 3.96% of cyclohexanone, 4.44% of intermediate components and 3.99% of X oil, the tower top pressure is 3-4 kPa, the reflux ratio is 32, the crude alcohol tower top distillate is continuously discharged at the speed of 480kg/h, the side line extraction liquid is continuously discharged into a crude alcohol tank at the speed of 11520kg/h, and the crude alcohol tower bottom liquid is continuously discharged at the speed of 500 kg/h. The top temperature is 45-55 ℃, the side line discharge temperature is 70-80 ℃, the kettle temperature is 110-160 ℃, the top distillate contains 98.08% of cyclohexanone, 1.22% of cyclohexanol, 0.70% of intermediate component, the side line discharge liquid contains 0.21% of cyclohexanone, 95.01% of cyclohexanol, 4.78% of intermediate component, the kettle liquid contains 0.25% of cyclohexanol, and 99.75% of other impurities such as X oil.
The crude alcohol material from the decompression tower contains 95.01% of cyclohexanol, 0.21% of cyclohexanone and 4.78% of intermediate component, and is fed into the decompression tower at the speed of 188.7kg/h, the pressure at the top of the tower is 3-4 kPa, the reflux ratio is 15, the distillate at the top of the decompression tower is continuously discharged at the speed of about 17.0kg/h, and the bottom liquid at the bottom of the decompression tower is continuously discharged at the speed of about 171.7 kg/h. The top temperature is 45-55 ℃, the kettle temperature is 85-100 ℃, the top distillate of the vacuum tower contains 67.21 percent of cyclohexanol, 2.33 percent of cyclohexanone and 30.46 percent of intermediate component, and the kettle liquid of the vacuum tower contains 97.76 percent of cyclohexanol and 2.24 percent of intermediate component. The feeding amount of the decompression tower is equal to 1.64% of the side effluent of the crude alcohol tower;
the tower top distillate of the vacuum tower is pumped to an atmospheric tower, the flow rate is 17.0kg/h, the reflux ratio is 15, the tower top distillate of the atmospheric tower is continuously discharged at a speed of about 12.0kg/h, and the tower bottom liquid of the atmospheric tower is continuously discharged at a speed of about 5.0 kg/h. The top temperature is 155-165 ℃, the kettle temperature is 200-220 ℃, the top distillate of the atmospheric tower contains 94.94% of cyclohexanol, 3.30% of cyclohexanone, 1.76% of intermediate component, and the kettle liquid of the atmospheric tower contains 0.78% of cyclohexanol and 99.22% of intermediate component. The feed to the atmospheric tower was equivalent to 0.15% of the crude alcohol column side offtake.
The crude alcohol composition before the method of this example was not employed was: cyclohexanol 80.40%, cyclohexanone 5.74%, impurity 13.86%; the process of this example was used and run to a composition stabilized cyclohexanol dehydrogenation feed composition of: 95.01% of cyclohexanol, 0.21% of cyclohexanone and 4.78% of intermediate components. The cyclohexanone removal rate was 96.3%, and the steam consumption required for cyclohexanone removal and cyclohexanol distillation was about 0.33t steam/t. The removal rate of the intermediate component was 65.6%, and the steam consumption required for the intermediate component removal was about 23.2t steam/t intermediate component.
Comparative example 1
The comparative example uses a reduced pressure-normal pressure double tower rectification to remove intermediate components:
the crude alcohol from the top of the alcohol tower in the original production device is introduced into a crude alcohol tank and mixed with refined alcohol to be used as the material for the dehydrogenation process of the cyclohexanol, and the flow is 12000kg/h. The crude alcohol tank material contained 91.22% cyclohexanol, 4.13% cyclohexanone and 4.65% intermediate component.
Feeding the crude alcohol to the middle part of a vacuum tower at the speed of 192.3kg/h for rectification separation, and returning the bottom liquid of the vacuum tower to a crude alcohol tank, wherein the flow is 168.3kg/h; the distillate at the top of the vacuum tower is continuously discharged to an atmospheric tower, and the flow is 24.0kg/h. The pressure at the top of the vacuum tower is 3-4 kPa, the reflux ratio is 15, the temperature at the top of the vacuum tower is 58-75 ℃, and the temperature at the bottom of the vacuum tower is 85-100 ℃. The distillate at the top of the vacuum tower contains 45.93 percent of cyclohexanol, 31.57 percent of cyclohexanone and 22.50 percent of intermediate component, and the kettle liquid of the vacuum tower contains 97.69 percent of cyclohexanol, 0.21 percent of cyclohexanone and 2.10 percent of intermediate component.
Sending the distillate at the top of the vacuum tower to the middle part of the normal pressure tower at the speed of 24kg/h for rectification separation, and returning the distillate at the top of the normal pressure tower to the crude alcohol tank or the crude alcohol ketone tank, wherein the flow is 19kg/h; and discharging the kettle liquid of the atmospheric tower to a waste liquid tank, wherein the flow is 5kg/h. The tower top pressure of the atmospheric tower is 90-110 kPa, the tower top temperature is 150-165 ℃, the tower bottom temperature is 200-220 ℃, and the reflux ratio is 15. The top distillate of the atmospheric tower contains 57.60 percent of cyclohexanol, 39.80 percent of cyclohexanone and 2.60 percent of intermediate component, and the bottom liquid of the atmospheric tower contains 1.50 percent of cyclohexanol, 0.22 percent of cyclohexanone and 98.28 percent of intermediate component.
The vacuum tower throughput was about 1.60% of the crude alcohol and the atmospheric tower throughput was about 0.2% of the crude alcohol. The crude alcohol composition before the method of this example was not employed was: cyclohexanol 80.40%, cyclohexanone 5.74%, impurity 13.86%; the crude alcohol composition after the procedure of this example and running to a stable composition was: 91.22% of cyclohexanol, 4.13% of cyclohexanone and 4.65% of intermediate components. The intermediate component content is greatly reduced, so that the cyclohexanone content in the ketone tower kettle liquid is reduced, and the indirect removal rate of cyclohexanone is 28%; the removal rate of the intermediate component was 66.5%, and the steam consumption required for the intermediate component removal was about 34.4t steam/t intermediate component.
Comparative example 2
The comparative example adopts normal pressure single tower rectification:
the crude alcohol from the top of the alcohol tower in the original production device is introduced into a crude alcohol tank and mixed with refined alcohol to be used as the material for the dehydrogenation process of the cyclohexanol, and the flow is 12000kg/h. The crude alcohol tank material contained 91.34% cyclohexanol, 4.12% cyclohexanone and 4.54% intermediate component.
The crude alcohol is directly sent to the middle part of the atmospheric tower for rectification separation at the speed of 185.5kg/h, and the distillate at the top of the atmospheric tower is returned to the crude alcohol tank with the flow of 180.5kg/h; and discharging the kettle liquid of the atmospheric tower to a waste liquid tank, wherein the flow is 5kg/h. The pressure at the top of the tower is 90-110 kPa, the temperature at the top of the tower is 150-165 ℃, the temperature at the bottom of the tower is 200-220 ℃, and the reflux ratio is 20. The top distillate of the atmospheric tower contains 93.94 percent of cyclohexanol, 4.23 percent of cyclohexanone, 1.83 percent of intermediate component, and the bottom liquid of the atmospheric tower contains 1.02 percent of cyclohexanol, 0.14 percent of cyclohexanone and 98.84 percent of intermediate component.
The normal pressure tower throughput is about 1.8% of the crude alcohol. The crude alcohol composition before the procedure of this comparative example was not used was: cyclohexanol 80.40%, cyclohexanone 5.74%, impurity 13.86%; the crude alcohol composition after the procedure of this example and running to a stable composition was: 91.34% of cyclohexanol, 4.12% of cyclohexanone and 4.54% of intermediate components. The intermediate component content is greatly reduced, so that the cyclohexanone content in the ketone tower kettle liquid is reduced, and the indirect removal rate of cyclohexanone is 28%; the removal rate of the intermediate component was 67.2%, and the steam consumption required for the intermediate component removal was about 189t steam/t intermediate component.
Comparative example 3
The comparative example adopts normal pressure single tower rectification:
the crude alcohol from the top of the alcohol tower in the original production device is introduced into a crude alcohol tank and mixed with refined alcohol to be used as the material for the dehydrogenation process of the cyclohexanol, and the flow is 12000kg/h. The crude alcohol tank material contains 89.77% of cyclohexanol, 4.35% of cyclohexanone and 5.88% of intermediate component.
The crude alcohol is directly sent to the middle part of the atmospheric tower for rectification separation at the speed of 181.8kg/h, and the distillate at the top of the atmospheric tower is returned to the crude alcohol tank with the flow of 174.5kg/h; and discharging the kettle liquid of the atmospheric tower to a waste liquid tank, wherein the flow is 7.3kg/h. The pressure at the top of the tower is 90-110 kPa, the temperature at the top of the tower is 150-165 ℃, the temperature at the bottom of the tower is 180-190 ℃, and the reflux ratio is 3. The top distillate of the atmospheric tower contains 92.24 percent of cyclohexanol, 4.50 percent of cyclohexanone, 3.26 percent of intermediate component, and the bottom liquid of the atmospheric tower contains 30.5 percent of cyclohexanol, 0.75 percent of cyclohexanone and 68.75 percent of intermediate component.
The normal pressure tower throughput is about 1.52% of the crude alcohol. The crude alcohol composition before the procedure of this comparative example was not used was: cyclohexanol 80.40%, cyclohexanone 5.74%, impurity 13.86%; the crude alcohol composition after the procedure of this example and running to a stable composition was: 89.77% of cyclohexanol, 4.35% of cyclohexanone and 5.88% of intermediate components. The content of cyclohexanone in the ketone tower kettle liquid is reduced to a certain extent due to the substantial reduction of the content of intermediate components, and the indirect removal rate of cyclohexanone is 24.2%; the amount of cyclohexanol lost was 0.44t/t of intermediate component, the removal rate of intermediate component was 57.6%, and the steam consumption required for intermediate component removal was about 175t of steam/t of intermediate component.
Comparative example 4
The comparative example adopts normal pressure single tower rectification:
the crude alcohol from the top of the alcohol tower in the original production device is introduced into a crude alcohol tank and mixed with refined alcohol to be used as the material for the dehydrogenation process of the cyclohexanol, and the flow is 12000kg/h. The crude alcohol tank material contained 89.83% cyclohexanol, 4.55% cyclohexanone and 5.62% intermediate component.
The crude alcohol is directly sent to the middle part of the atmospheric tower for rectification separation at the speed of 169kg/h, and the distillate at the top of the atmospheric tower is returned to the crude alcohol tank with the flow of 160.5kg/h; and discharging the kettle liquid of the atmospheric tower to a waste liquid tank, wherein the flow is 8.5kg/h. The pressure at the top of the tower is 90-110 kPa, the temperature at the top of the tower is 150-165 ℃, the temperature at the bottom of the tower is 170-180 ℃, and the reflux ratio is 5. The top distillate of the atmospheric tower contains 92.48 percent of cyclohexanol, 4.72 percent of cyclohexanone, 2.80 percent of intermediate component, and the bottom liquid of the atmospheric tower contains 39.48 percent of cyclohexanol, 1.32 percent of cyclohexanone and 59.20 percent of intermediate component.
The normal pressure tower throughput is about 1.41% of the crude alcohol. The crude alcohol composition before the procedure of this comparative example was not used was: cyclohexanol 80.40%, cyclohexanone 5.74%, impurity 13.86%; the crude alcohol composition after the procedure of this example and running to a stable composition was: 89.83% of cyclohexanol, 4.55% of cyclohexanone and 5.62% of intermediate component. The intermediate component content is greatly reduced, so that the cyclohexanone content in the ketone tower kettle liquid is reduced, and the indirect removal rate of cyclohexanone is 20.7%; the amount of cyclohexanol lost was 0.67t/t of intermediate component, the removal rate of intermediate component was 59.5%, and the steam consumption required for intermediate component removal was about 241t of steam/t of intermediate component.
Example 3
The material of the cyclohexanol dehydrogenation procedure of the crude alcohol tank after stable operation of the process of example 2 is adopted, a cyclohexanol dehydrogenation test is carried out in a cyclohexanol dehydrogenation reactor, the catalyst is Zn-Ca, the reaction temperature is 380 ℃, the reaction pressure is 0.16MPa (absolute pressure), and the liquid hourly space velocity is 0.85h -1 The material of the cyclohexanol dehydrogenation process contains 95.01% of cyclohexanol, 0.21% of cyclohexanone and 4.78% of intermediate component, and the dehydrogenation product contains 26.32% of cyclohexanol, 68.13% of cyclohexanone, 5.55% of other components, 68.69% of cyclohexanol conversion, 67.92% of cyclohexanone and 98.88% of cyclohexanone selectivity.
Comparative example 5
Materials in a crude alcohol tank in the existing device are used as raw materials, a cyclohexanol dehydrogenation test is carried out in a cyclohexanol dehydrogenation reactor, a catalyst is Zn-Ca, the reaction temperature is 380 ℃, the reaction pressure is 0.16MPa (absolute pressure), and the liquid hourly space velocity is 0.85h -1 The raw materials comprise 80.40% of cyclohexanol, 5.74% of cyclohexanone, 13.86% of intermediate component, 21.82% of cyclohexanol, 61.64% of cyclohexanone, 16.54% of other components, 58.58% of cyclohexanol conversion, 55.90% of cyclohexanone increase and 95.43% of cyclohexanone selectivity.
Comparative example 6
By usingThe material of the cyclohexanol dehydrogenation process of the crude alcohol tank after stable operation of the process of comparative example 1 was subjected to a cyclohexanol dehydrogenation test in a cyclohexanol dehydrogenation reactor, the catalyst was Zn-Ca, the reaction temperature was 380 ℃, the reaction pressure was 0.16MPa (absolute pressure), and the liquid hourly space velocity was 0.85h -1 The material of the cyclohexanol dehydrogenation process contains 91.22% of cyclohexanol, 4.13% of cyclohexanone and 4.65% of intermediate component, and the dehydrogenation product contains 25.46% of cyclohexanol, 67.88% of cyclohexanone, 6.66% of other components, 65.76% of cyclohexanol conversion, 63.75% of cyclohexanone increase and 96.94% of cyclohexanone selectivity.
Comparative example 7
The material of the cyclohexanol dehydrogenation procedure of the crude alcohol tank after stable operation of the process of comparative example 3 is adopted, a cyclohexanol dehydrogenation test is carried out in a cyclohexanol dehydrogenation reactor, the catalyst is Zn-Ca, the reaction temperature is 380 ℃, the reaction pressure is 0.16MPa (absolute pressure), and the liquid hourly space velocity is 0.85h -1 The material of the dehydrogenation process of the cyclohexanol contains 89.77 percent of cyclohexanol, 4.35 percent of cyclohexanone and 5.88 percent of intermediate component, and the dehydrogenation product contains 24.86 percent of cyclohexanol, 67.07 percent of cyclohexanone, 8.07 percent of other components, 64.91 percent of cyclohexanol conversion and 62.72 percent of cyclohexanone increase and 96.63 percent of cyclohexanone selectivity.
The above embodiments are illustrative of the present invention and not limiting the invention, it will be appreciated by those skilled in the art that the present invention is not limited to the above embodiments, but rather the above embodiments and description merely illustrate the specific working principles of the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (7)
1. A process for removing cyclohexanone and intermediate components in cyclohexanol, comprising the steps of:
1) Rectifying ketone tower bottom liquid in a crude alcohol tower with a side line, returning crude alcohol tower top distillate to the crude alcohol ketone tank, feeding the side line extraction liquid into the crude alcohol tank, and discharging crude alcohol tower bottom liquid X oil;
2) Leading out crude alcohol from the crude alcohol tank to a vacuum tower for vacuum rectification, enabling distillate at the top of the vacuum tower to enter an atmospheric tower, and enabling kettle liquid of the vacuum tower to return to the crude alcohol tank;
3) The tower top distillate of the vacuum tower is subjected to normal pressure rectification separation in an atmospheric tower, the tower top distillate of the atmospheric tower is returned to the crude alcohol tank, and the tower bottom liquid of the atmospheric tower is discharged;
the pressure at the top of the crude alcohol tower is 1-10 kPa, and the reflux ratio is 10-100;
in the step 2), the pressure at the top of the vacuum tower is 1-10 kPa, the reflux ratio is 5-20, the temperature at the top of the vacuum tower is 40-100 ℃, and the temperature at the bottom of the vacuum tower is 60-120 ℃;
in the step 3), the pressure at the top of the atmospheric tower is normal pressure, the reflux ratio is 5-20, the temperature at the top of the atmospheric tower is 150-165 ℃, and the temperature at the bottom of the atmospheric tower is 200-220 ℃.
2. The method according to claim 1, characterized in that: in the step 1), the crude alcohol tower is a baffle rectifying tower.
3. The method according to claim 1, characterized in that: cyclohexanone is used as a main material in the distillate at the top of the crude alcohol tower, and the total content of cyclohexanol and intermediate components is not higher than 3%; the side-stream extraction liquid is mainly cyclohexanol, and the total content of cyclohexanone and X oil is not higher than 2%; the crude alcohol tower bottom liquid takes X oil as main component, and the total content of cyclohexanone and cyclohexanol is not higher than 2%.
4. The method according to claim 1, characterized in that: in the step 2), the crude alcohol material amount of the decompression tower which is led out from the crude alcohol tank is 1 to 10 weight percent of the liquid amount of the side line of the crude alcohol tower.
5. The method according to claim 1, characterized in that: the total content of intermediate components in the tower top distillate of the vacuum tower is not less than 20 percent, and the total content of intermediate components in the tower bottom liquid of the vacuum tower is not more than 3 percent.
6. The method according to claim 1, characterized in that: in the step 3), the reflux ratio of the atmospheric tower is 10-15, and the temperature of the tower kettle is 205-215 ℃.
7. The method according to claim 1 or 6, characterized in that: the total content of intermediate components in the distillate at the top of the atmospheric tower is not higher than 3%, and the content of cyclohexanol in the kettle liquid of the atmospheric tower is not higher than 3%.
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