CN110563552A - Comprehensive utilization method of cyclohexanone light oil - Google Patents
Comprehensive utilization method of cyclohexanone light oil Download PDFInfo
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
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Abstract
The invention relates to a comprehensive utilization method for producing light oil from cyclohexanone, belonging to the field of fine chemical engineering. And (2) removing water from the light oil, then carrying out hydrogenation reduction, rectifying the hydrogenated light oil, separating cyclohexanol, n-pentanol and cyclopentanol, and feeding the separated cyclohexanol into a dehydrogenation tower. Dehydrogenating to obtain cyclohexanone crude product, and feeding the cyclohexanone crude product to a cyclohexanone refining system; the n-amyl alcohol and cyclopentanol are used as fuel to go to a cyclohexanone waste alkali incineration device. The method of the invention can recover the components with economic value in the light oil, reduce the production cost, improve the economic benefit and reduce the environmental pollution.
Description
Technical Field
The invention relates to a comprehensive utilization method for producing light oil from cyclohexanone, belonging to the field of fine chemical engineering.
Background
The cyclohexane air oxidation method for preparing cyclohexanone is the most widely applied production process in cyclohexanone production, and 2-5% of by-products with low boiling points, commonly called light oil, can be generated in the production process, wherein the by-products are rich in cyclohexane, cyclohexanone and epoxy cyclohexane, and also contain n-amyl alcohol, cyclopentanol and other impurities. The method has practical significance for the research of recycling of the light oil, and can not only recycle the components with economic value in the light oil to reduce the production cost, but also reduce the environmental pollution.
CN1331077A discloses a method for separating cyclohexene oxide from light oil, which is characterized in that the cyclohexene oxide in the light oil is converted into 2-halogenated cyclohexanol with a higher boiling point, then low boiling point substances are separated, the 2-halogenated cyclohexanol is reduced into cyclohexene oxide through cyclization, and the cyclohexene oxide is obtained through rectification and refining.
CN101225077A discloses a novel ring-opening reaction method for a process of recovering cyclohexene oxide from light oil, which comprises the following steps: the method comprises the steps of carrying out ring-opening reaction on light oil containing epoxy cyclohexane components and hydrochloric acid to separate other components of the light oil from high-boiling 2-chlorocyclohexanol, carrying out ring-closing reaction on the separated collected 2-chlorocyclohexanol and alkali, and rectifying to obtain epoxy cyclohexane, wherein the hydrochloric acid is used in a salt water solution or in a gas state, and the hydrolysis is inhibited by adding salt into the hydrochloric acid or hydrochloric acid gas is not taken into water, so that the problems of hydrolysis side reaction and the like in process production are solved.
CN1106784A discloses a method for recovering n-pentanol and cyclohexene oxide from light oil, which is a byproduct of cyclohexanol and cyclohexanone preparation by cyclohexane oxidation, and the patent is characterized in that: adopting water and cyclohexene oxide in light oil to form binary azeotrope, evaporating crude cyclohexene oxide at 88-90.5 ℃, and adding an organic entrainer to refine to obtain the cyclohexene oxide, wherein the purity can reach 95%, and the recovery rate is more than or equal to 70%; n-amyl alcohol is distilled out at 135 ℃ and 137 ℃, the purity is more than or equal to 95 percent, and the recovery rate is more than or equal to 70 percent. The process is simple, but the product purity can not meet the commodity requirement, and the recovery rate is not high.
At present, research on cyclohexanone light oil focuses on purifying and refining components with higher economic values such as the cyclohexanone and the n-amyl alcohol in the light oil and recycling the components. However, the boiling points of the epoxy cyclohexane, the n-amyl alcohol and other components are close to the boiling points of impurity components in the light oil, and a high-purity product is difficult to obtain by a conventional rectification method, so that the commercial index cannot be reached. The technical means of converting the cyclohexene oxide into high boiling point substances by chemical means and then separating the substances has the problems of impurity introduction, complex operation and easy environmental pollution.
Disclosure of Invention
Because the components in the light oil are complex and have relatively close boiling points, the light oil is difficult to refine and purify to obtain a high-purity byproduct, the invention aims to not refine and separate the epoxycyclohexane, the n-amyl alcohol, the cyclopentanol and other components in the light oil, but to carry out hydrogenation conversion on the useful components of the light oil to convert the useful components into high-boiling cyclohexanol, and the separated cyclohexanol can enter a cyclohexanone production system.
The light oil treated by the method is a byproduct generated in cyclohexanone production, wherein the content of cyclohexanone is 20-40%, the content of epoxy cyclohexane is 30-60%, the content of n-amyl alcohol and cyclopentanol is 5-10%, the content of water is 1-10%, the content of cyclohexane is 1-10%, and the content of the rest substances is 1-5% in percentage by mass.
The light oil is first dewatered, because 1, 2-dihydroxycyclohexanol is produced in hydrogenation process if water is contained, and the reduction selectivity is seriously affected, so that anhydrous Raney nickel catalyst or palladium carbon catalyst is also selected as hydrogenation catalyst. The operating pressure of the water removal tower is normal pressure, the operating temperature is 110-120 ℃, and the reflux ratio is 1: 1-10: 1, enabling the tower top wastewater to enter a wastewater tank and go to a wastewater treatment system, wherein the wastewater contains low-boiling-point impurities such as cyclohexane and the like.
And (3) carrying out hydrogenation reduction on the light oil after water removal, wherein a fixed bed reactor is adopted, and a hydrogenation catalyst is an anhydrous Raney nickel catalyst or a palladium carbon catalyst. When using anhydrous Raney nickel catalyst, the reaction temperature is 80-120 ℃, the retention time is 4-8h, and the hydrogen-oil ratio is 2: 1-6: 1. reaction pressure is 2-6Mpa, conversion rate is 96-100%, and selectivity is 92-96%; when a palladium-carbon catalyst is used, the reaction temperature is 60-100 ℃, the retention time is 2-4h, and the hydrogen-oil ratio is 2: 1-6: 1. reaction pressure is 2-6Mpa, conversion rate is 98-100%, and selectivity is 94-98%.
And (3) introducing the hydrogenated light oil into a separation tower, wherein the operation temperature is 70-80 ℃, the operation vacuum degree is 95-100kpa, and the reflux ratio is 1: 1-20: 1, separating n-pentanol and cyclopentanol from the top of the tower, and obtaining cyclohexanol from the bottom of the tower. And (4) feeding the cyclohexanol obtained after separation into a dehydrogenation tower, and preparing a cyclohexanone crude product to a cyclohexanone refining system after dehydrogenation. The dehydrogenation tower adopts CuO-ZnO/Al2O3The catalyst has a reaction temperature of 220 ℃ and 280 ℃ and a reaction space velocity of 0.5-1h-1The conversion rate is 85-90%, the selectivity is 95-99%, and the cyclohexanone crude product is prepared. The n-amyl alcohol cyclopentanol material separated from the top of the tower contains impurities with similar boiling points, and the refining energy consumption is higher, and the n-amyl alcohol cyclopentanol material is used as fuel and sent to a cyclohexanone waste alkali incineration device.
The method of the invention can recover the components with economic value in the light oil, reduce the production cost, improve the economic benefit and reduce the environmental pollution.
Drawings
FIG. 1 is a schematic process flow diagram of a method according to an embodiment of the present invention.
Detailed Description
The technical solution of the present invention is further explained below with reference to the examples and the accompanying drawings.
The process flow of the following example method refers to figure 1.
Example 1
10 ten thousand tons/year cyclohexanone production device produces 600t of light oil annually, wherein the average content of cyclohexanone is 40%, the content of epoxy cyclohexane is 40%, the content of n-amyl alcohol and cyclopentanol is 10%, the content of water is 5%, the content of cyclohexane is 2%, and the content of other substances is 3%.
The operating pressure of the water removing tower is normal pressure, the operating temperature is 110 ℃, and the reflux ratio is 10: 1, enabling the tower top wastewater to enter a wastewater tank and go to a wastewater treatment system, wherein the wastewater contains low-boiling-point impurities such as cyclohexane and the like. And (2) carrying out hydrogenation reduction on the light oil after water removal, wherein a fixed bed reactor is adopted, the hydrogenation catalyst is an anhydrous Raney nickel catalyst, the reaction temperature is 120 ℃, the retention time is 4h, and the hydrogen-oil ratio is 2: 1. the reaction pressure is 2Mpa, the conversion rate is 96 percent, and the selectivity is 92 percent;
And (3) rectifying the hydrogenated light oil in a light 1 tower at an operation temperature of 70 ℃, an operation vacuum degree of 100kpa and a reflux ratio of 20: 1, separating n-pentanol and cyclopentanol from the top of the tower, and obtaining cyclohexanol from the bottom of the tower. And (4) feeding the cyclohexanol obtained after separation into a dehydrogenation tower, and preparing a cyclohexanone crude product to a cyclohexanone refining system after dehydrogenation. The dehydrogenation tower adopts CuO-ZnO/Al2O3Catalyst, reaction temperature is 220 ℃, and reaction space velocity is 1h-1The conversion rate is 90 percent, the selectivity is 99 percent, and a cyclohexanone crude product is prepared. The n-amyl alcohol cyclopentanol material separated from the top of the tower contains impurities with similar boiling points, and the refining energy consumption is higher, and the n-amyl alcohol cyclopentanol material is used as fuel and sent to a cyclohexanone waste alkali incineration device.
This example increases cyclohexanone production by 450 tons/year, price 12000 yuan/ton, 540 ten thousand yuan/year for the production equipment. The investment cost of the device is 100 ten thousand yuan/year, the energy consumption and material consumption cost is 50 ten thousand yuan/year, the labor cost is 60 ten thousand yuan/year, the accumulated cost is 210 ten thousand yuan/year, and the economic benefit is 330 ten thousand yuan/year.
Comparative example 1
10 ten thousand tons/year cyclohexanone production device produces 600t of light oil annually, wherein the average content of cyclohexanone is 40%, the content of epoxy cyclohexane is 40%, the content of n-amyl alcohol and cyclopentanol is 10%, the content of water is 5%, the content of cyclohexane is 2%, and the content of other substances is 3%.
The produced light oil is sold as a byproduct, the price is 2000 yuan/ton, and the economic benefit is 120 ten thousand yuan/year.
Comparative example 2
10 ten thousand tons/year cyclohexanone production device produces 600t of light oil annually, wherein the average content of cyclohexanone is 40%, the content of epoxy cyclohexane is 40%, the content of n-amyl alcohol and cyclopentanol is 10%, the content of water is 5%, the content of cyclohexane is 2%, and the content of other substances is 3%.
Firstly, rectifying light oil to recover cyclohexanone, mixing the rectified light oil, hydrochloric acid and salt, and carrying out ring-opening reaction at 80 ℃ to respectively obtain an oil-water mixture of 2-chlorocyclohexanol and n-amyl alcohol, wherein the concentration of the salt water is 20%, and the molar ratio of epoxy cyclohexane to hydrogen chloride in hydrochloric acid is 1: 10. the ring opening reaction generates 2-chlorocyclohexanol with high boiling point, which is separated from n-pentanol by rectification after oil-water separation to recover n-pentanol. The absolute pressure in the rectifying tower is 100lpa, the temperature is 150 ℃, n-amyl alcohol is removed from the top of the rectifying tower, and 2-chlorocyclohexane flows out from the bottom of the rectifying tower. Mixing the 2-chlorocyclohexanol with liquid alkali in a closed-loop reactor, performing closed-loop reaction at 130 ℃ to respectively obtain cyclohexene oxide and circulating brine, and performing oil-water separation to obtain the cyclohexene oxide.
N-pentanol and cyclohexene oxide are sold as by-products respectively, wherein the n-pentanol has the purity of about 50 tons/year, the purity of 95 percent and the price of 15000 yuan/ton; the epoxy cyclohexane is about 200 tons/year, the purity is 95 percent, and the price is 5000 yuan/ton; the cyclohexanone is recovered by about 200 tons/year, the purity is 99 percent, and the price is 12000 yuan/ton. The by-product sales amounted to 415 ten thousand yuan per year. The investment cost of the device is 100 ten thousand yuan/year, the energy consumption and material consumption cost is 80 ten thousand yuan/year, the labor cost is 60 ten thousand yuan/year, the accumulated cost is 190 ten thousand yuan/year, and the economic benefit is 225 ten thousand yuan/year.
Example 2
The 6 ten thousand ton/year cyclohexanone production device produces 500t of light oil annually, wherein the cyclohexanone content is 30%, the epoxy cyclohexane content is 50%, the n-amyl alcohol and cyclopentanol content is 8%, the water content is 5%, the cyclohexane content is 2%, and the content of other substances is 5%.
The operating pressure of the water removing tower is normal pressure, the operating temperature is 120 ℃, and the reflux ratio is 1: 1, enabling the tower top wastewater to enter a wastewater tank and go to a wastewater treatment system, wherein the wastewater contains low-boiling-point impurities such as cyclohexane and the like. And (3) carrying out hydrogenation reduction on the light oil after water removal, wherein a fixed bed reactor is adopted, and a hydrogenation catalyst is a palladium-carbon catalyst. When a palladium-carbon catalyst is used, the reaction temperature is 100 ℃, the retention time is 2h, and the hydrogen-oil ratio is 6: 1. reaction pressure 2Mpa, conversion rate 100% and selectivity 98%.
And (3) rectifying the hydrogenated light oil in a light 1 tower at the operating temperature of 80 ℃, the operating vacuum degree of 95kpa and the reflux ratio of 20: 1, separating n-pentanol and cyclopentanol from the top of the tower, and obtaining cyclohexanol from the bottom of the tower. And (4) feeding the cyclohexanol obtained after separation into a dehydrogenation tower, and preparing a cyclohexanone crude product to a cyclohexanone refining system after dehydrogenation. The dehydrogenation tower adopts CuO-ZnO/Al2O3Catalyst, reaction temperature 220 ℃, reaction space velocity 0.5h-1The conversion rate is 90 percent, the selectivity is 95 percent, and a cyclohexanone crude product is prepared. The n-amyl alcohol cyclopentanol material separated from the top of the tower contains impurities with similar boiling points, and the refining energy consumption is higher, and the n-amyl alcohol cyclopentanol material is used as fuel and sent to a cyclohexanone waste alkali incineration device.
Example 3
10 ten thousand tons/year cyclohexanone production device produces 800t of light oil annually, wherein the cyclohexanone content is 20 percent, the epoxy cyclohexane content is 60 percent, the n-amyl alcohol and cyclopentanol content is 10 percent, the water content is 5 percent, the cyclohexane content is 3 percent, and the content of other substances is 2 percent.
Firstly, removing water from light oil, wherein the operating pressure of a water removal tower is normal pressure, the operating temperature is 115 ℃, and the reflux ratio is 1: 5, the wastewater at the top of the tower enters a wastewater tank to go to a wastewater treatment system, and the wastewater contains low-boiling-point impurities such as cyclohexane and the like. And (3) carrying out hydrogenation reduction on the light oil after water removal, wherein a fixed bed reactor is adopted, and the hydrogenation catalyst is an anhydrous Raney nickel catalyst. When an anhydrous Raney nickel catalyst is used, the reaction temperature is 80 ℃, the retention time is 8h, and the hydrogen-oil ratio is 6: 1. the reaction pressure is 6Mpa, the conversion rate is 96 percent, and the selectivity is 96 percent.
And (3) rectifying the hydrogenated light oil in a light 1 tower at the operating temperature of 80 ℃, the operating vacuum degree of 95-100kpa and the reflux ratio of 1: 1-20: 1, separating n-pentanol and cyclopentanol from the top of the tower, and obtaining cyclohexanol from the bottom of the tower. And (4) feeding the cyclohexanol obtained after separation into a dehydrogenation tower, and preparing a cyclohexanone crude product to a cyclohexanone refining system after dehydrogenation. The dehydrogenation tower adopts CuO-ZnO/Al2O3The catalyst is used, the reaction temperature is 250 ℃, and the reaction space velocity is 1h-1The conversion rate is 88 percent, the selectivity is 96 percent, and a cyclohexanone crude product is prepared. The n-amyl alcohol cyclopentanol material separated from the top of the tower contains impurities with similar boiling points, and the refining energy consumption is higher, and the n-amyl alcohol cyclopentanol material is used as fuel and sent to a cyclohexanone waste alkali incineration device.
Example 4
8 ten thousand tons/year cyclohexanone production device, produce 600t of light oil annually, wherein cyclohexanone content 40%, epoxy cyclohexane content 30%, n-pentanol and cyclopentanol content 10%, water content 5%, cyclohexane content 10%, the content of the other substances 5%.
The operating pressure of the water removing tower is normal pressure, the operating temperature is 120 ℃, and the reflux ratio is 1: 3, the wastewater at the top of the tower enters a wastewater tank to go to a wastewater treatment system, and the wastewater contains low-boiling-point impurities such as cyclohexane and the like. And (3) carrying out hydrogenation reduction on the light oil after water removal, wherein a fixed bed reactor is adopted, and a hydrogenation catalyst is a palladium-carbon catalyst. When a palladium-carbon catalyst is used, the reaction temperature is 100 ℃, the retention time is 3h, and the hydrogen-oil ratio is 4: 1. reaction pressure 3Mpa, conversion rate 99% and selectivity 98%.
And (3) rectifying the hydrogenated light oil in a light 1 tower at the operating temperature of 80 ℃, the operating vacuum degree of 95kpa and the reflux ratio of 10: 1, separating n-pentanol and cyclopentanol from the top of the tower, and obtaining cyclohexanol from the bottom of the tower. And (4) feeding the cyclohexanol obtained after separation into a dehydrogenation tower, and preparing a cyclohexanone crude product to a cyclohexanone refining system after dehydrogenation. The dehydrogenation tower adopts CuO-ZnO/Al2O3The catalyst is used, the reaction temperature is 230 ℃, and the reaction space velocity is 0.6h-1The conversion rate is 86 percent, the selectivity is 97 percent, and a cyclohexanone crude product is prepared. The n-amyl alcohol cyclopentanol material separated from the top of the tower contains impurities with similar boiling points, and the refining energy consumption is higher, and the n-amyl alcohol cyclopentanol material is used as fuel and sent to a cyclohexanone waste alkali incineration device.
Example 5
10 ten thousand tons/year cyclohexanone production device produces 600t of light oil annually, wherein the cyclohexanone content is 30 percent, the epoxy cyclohexane content is 40 percent, the n-pentanol and cyclopentanol content is 10 percent, the water content is 10 percent, the cyclohexane content is 8 percent, and the content of other substances is 2 percent.
Firstly, removing water from light oil, wherein the operating pressure of a water removal tower is normal pressure, the operating temperature is 115 ℃, and the reflux ratio is 1: 4, the wastewater at the top of the tower enters a wastewater tank to go to a wastewater treatment system, and the wastewater contains low-boiling-point impurities such as cyclohexane and the like. And (3) carrying out hydrogenation reduction on the light oil after water removal, wherein a fixed bed reactor is adopted, and the hydrogenation catalyst is an anhydrous Raney nickel catalyst. When an anhydrous Raney nickel catalyst is used, the reaction temperature is 90 ℃, the retention time is 6h, and the hydrogen-oil ratio is 4: 1. reaction pressure 4Mpa, conversion rate 97% and selectivity 96%.
And (3) rectifying the hydrogenated light oil in a light 1 tower at the operating temperature of 75 ℃, the operating vacuum degree of 96kpa and the reflux ratio of 1: 7, separating n-pentanol and cyclopentanol at the top of the tower, and obtaining cyclohexanol at the bottom of the tower. And (4) feeding the cyclohexanol obtained after separation into a dehydrogenation tower, and preparing a cyclohexanone crude product to a cyclohexanone refining system after dehydrogenation. The dehydrogenation tower adopts CuO-ZnO/Al2O3Catalyst, reaction temperature is 240 ℃, and reaction space velocity is 1h-1The conversion rate is 90 percent, the selectivity is 95 percent, and a cyclohexanone crude product is prepared. The n-amyl alcohol cyclopentanol material separated from the top of the tower contains impurities with similar boiling points, and the refining energy consumption is higher, and the n-amyl alcohol cyclopentanol material is used as fuel and sent to a cyclohexanone waste alkali incineration device.
Example 6
10 ten thousand tons/year cyclohexanone production device produces 400t of light oil annually, wherein the cyclohexanone content is 20 percent, the epoxy cyclohexane content is 45 percent, the n-pentanol and cyclopentanol content is 10 percent, the water content is 10 percent, the cyclohexane content is 10 percent, and the content of other substances is 5 percent.
Firstly, removing water from light oil, wherein the operating pressure of a water removal tower is normal pressure, the operating temperature is 110 ℃, and the reflux ratio is 1: and 6, enabling the tower top wastewater to enter a wastewater tank to go to a wastewater treatment system, wherein the wastewater contains low-boiling-point impurities such as cyclohexane and the like.
And (3) carrying out hydrogenation reduction on the light oil after water removal, wherein a fixed bed reactor is adopted, and a hydrogenation catalyst is an anhydrous Raney nickel catalyst or a palladium carbon catalyst. When an anhydrous Raney nickel catalyst is used, the reaction temperature is 100 ℃, the retention time is 6h, and the hydrogen-oil ratio is 24: 1. reaction pressure 4Mpa, conversion rate 98% and selectivity 95%.
And (3) rectifying the hydrogenated light oil in a light 1 tower at the operating temperature of 75 ℃, the operating vacuum degree of 98kpa and the reflux ratio of 1: 12, separating n-pentanol and cyclopentanol at the top of the tower, and obtaining cyclohexanol at the bottom of the tower. And (4) feeding the cyclohexanol obtained after separation into a dehydrogenation tower, and preparing a cyclohexanone crude product to a cyclohexanone refining system after dehydrogenation. The dehydrogenation tower adopts CuO-ZnO/Al2O3Catalyst, reaction temperature is 260 ℃, and reaction space velocity is 0.7h-1The conversion rate is 89%, the selectivity is 98%, and a cyclohexanone crude product is prepared. The n-pentanol cyclopentanol material separated from the tower top contains impurities with similar boiling points, has higher energy consumption for refining again, and is sent to as fuelCyclohexanone waste alkali incineration device.
Example 7
A12-ten-thousand-ton/year cyclohexanone production device produces 1000t of light oil annually, wherein the cyclohexanone content is 40%, the epoxy cyclohexane content is 30%, the n-amyl alcohol and cyclopentanol content is 8%, the water content is 10%, the cyclohexane content is 8%, and the content of other substances is 4%.
The operating pressure of the water removing tower is normal pressure, the operating temperature is 120 ℃, and the reflux ratio is 1: 2, the wastewater at the top of the tower enters a wastewater tank and goes to a wastewater treatment system, and the wastewater contains low-boiling-point impurities such as cyclohexane and the like. And (3) carrying out hydrogenation reduction on the light oil after water removal, wherein a fixed bed reactor is adopted, and a hydrogenation catalyst is a palladium-carbon catalyst. When a palladium-carbon catalyst is used, the reaction temperature is 100 ℃, the retention time is 4h, and the hydrogen-oil ratio is 5: 1. reaction pressure 2Mpa, conversion rate 100% and selectivity 99%.
And (3) rectifying the hydrogenated light oil in a light 1 tower at the operating temperature of 80 ℃, the operating vacuum degree of 96kpa and the reflux ratio of 6: 1, separating n-pentanol and cyclopentanol from the top of the tower, and obtaining cyclohexanol from the bottom of the tower. And (4) feeding the cyclohexanol obtained after separation into a dehydrogenation tower, and preparing a cyclohexanone crude product to a cyclohexanone refining system after dehydrogenation. The dehydrogenation tower adopts CuO-ZnO/Al2O3Catalyst, reaction temperature 240 ℃, reaction space velocity 0.8h-1The conversion rate is 88 percent, the selectivity is 98 percent, and a cyclohexanone crude product is prepared. The n-amyl alcohol cyclopentanol material separated from the top of the tower contains impurities with similar boiling points, and the refining energy consumption is higher, and the n-amyl alcohol cyclopentanol material is used as fuel and sent to a cyclohexanone waste alkali incineration device.
Claims (10)
1. A comprehensive utilization method of cyclohexanone light oil is characterized in that the light oil is subjected to hydrogenation reduction after water removal, the hydrogenated light oil is rectified to separate cyclohexanol, n-amyl alcohol and cyclopentanol, the cyclohexanol obtained after separation enters a dehydrogenation tower, and a cyclohexanone crude product is prepared after dehydrogenation and goes to a cyclohexanone refining system.
2. The comprehensive utilization method of cyclohexanone light oil as claimed in claim 1, characterized in that the treated cyclohexanone light oil contains 20-40% of cyclohexanone, 30-60% of cyclohexene oxide, 5-10% of n-amyl alcohol and cyclopentanol, 1-5% of water, 1-5% of cyclohexane and 1-5% of the rest substances.
3. The method for comprehensively utilizing cyclohexanone light oil as claimed in claim 1, wherein the cyclohexanone light oil is subjected to a water removal operation before being treated, the operation pressure of a water removal tower is normal pressure, the operation temperature is 110-: 1-10: 1, enabling the wastewater at the top of the tower to enter a wastewater tank and go to a wastewater treatment system, and enabling anhydrous light oil at the bottom of the tower to enter a hydrogenation reactor.
4. The method for comprehensively utilizing cyclohexanone light oil according to claim 3, characterized in that a fixed bed reactor is adopted in the hydrogenation reduction of the anhydrous light oil, and an anhydrous Raney nickel catalyst is adopted as a hydrogenation catalyst.
5. The method for comprehensively utilizing cyclohexanone light oil according to claim 4, characterized in that when an anhydrous Raney nickel catalyst is adopted, the reaction temperature is 80-120 ℃, the retention time is 4-8h, and the hydrogen-oil ratio is 2: 1-6: 1. the reaction pressure is 2-6 MPa.
6. The method for comprehensively utilizing cyclohexanone light oil according to claim 3, characterized in that a fixed bed reactor is adopted during hydrogenation reduction of the anhydrous light oil, and a palladium-carbon catalyst can be adopted as a hydrogenation catalyst.
7. The method for comprehensively utilizing cyclohexanone light oil according to claim 6, characterized in that when a palladium-carbon catalyst is adopted, the reaction temperature is 60-100 ℃, the retention time is 2-4h, and the hydrogen-oil ratio is 2: 1-6: 1. the reaction pressure is 2-6 MPa.
8. The method for comprehensively utilizing cyclohexanone light oil according to claim 3, characterized in that the anhydrous light oil is hydrogenated and then enters a separation tower, the operation temperature is 70-80 ℃, the operation vacuum degree is 95-100kpa, and the reflux ratio is 1-20: 1, separating the materials of n-amyl alcohol and cyclopentanol from the top of the tower, obtaining cyclohexanol from the bottom of the tower, and enabling the materials of n-amyl alcohol and cyclopentanol to go to a cyclohexanone waste alkali incineration device for use as fuel.
9. The method for comprehensively utilizing cyclohexanone light oil as claimed in claim 8, wherein cyclohexanol is separated in a separation tower and then enters a dehydrogenation tower, and the dehydrogenation tower adopts CuO-ZnO/Al2O3The catalyst has a reaction temperature of 220 ℃ and 280 ℃ and a reaction space velocity of 0.5-1h-1The conversion rate is 85-90%, the selectivity is 95-99%, and the cyclohexanone crude product is prepared.
10. the method for comprehensively utilizing cyclohexanone light oil according to claim 9, characterized in that the crude cyclohexanone product obtained after dehydrogenation is fed into a cyclohexanone refining system in a cyclohexanone production system for refining.
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