CN115025722B - Equipment and method for producing cyclic ketone by oxidizing cyclic olefin with nitrous oxide - Google Patents
Equipment and method for producing cyclic ketone by oxidizing cyclic olefin with nitrous oxide Download PDFInfo
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- CN115025722B CN115025722B CN202210734540.7A CN202210734540A CN115025722B CN 115025722 B CN115025722 B CN 115025722B CN 202210734540 A CN202210734540 A CN 202210734540A CN 115025722 B CN115025722 B CN 115025722B
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- fixed bed
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- nitrous oxide
- cycloolefin
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- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 title claims abstract description 298
- 239000001272 nitrous oxide Substances 0.000 title claims abstract description 139
- 150000003997 cyclic ketones Chemical class 0.000 title claims abstract description 43
- -1 cyclic olefin Chemical class 0.000 title claims abstract description 34
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 103
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 99
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 239000000203 mixture Substances 0.000 claims abstract description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000011148 porous material Substances 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 27
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 229960001730 nitrous oxide Drugs 0.000 claims description 144
- 239000002151 riboflavin Substances 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 26
- 239000004149 tartrazine Substances 0.000 claims description 20
- 238000009826 distribution Methods 0.000 claims description 14
- 238000001819 mass spectrum Methods 0.000 claims description 12
- 235000013842 nitrous oxide Nutrition 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000003491 array Methods 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000004587 chromatography analysis Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000005373 porous glass Substances 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims description 2
- 238000004880 explosion Methods 0.000 abstract description 8
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 111
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 94
- 230000001105 regulatory effect Effects 0.000 description 33
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 32
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 32
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 28
- 238000005070 sampling Methods 0.000 description 21
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 18
- 239000000112 cooling gas Substances 0.000 description 17
- 238000004451 qualitative analysis Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 238000001514 detection method Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000004949 mass spectrometry Methods 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000005191 phase separation Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000010425 asbestos Substances 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910052895 riebeckite Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- TYDSIOSLHQWFOU-UHFFFAOYSA-N 2-cyclohexylidenecyclohexan-1-one Chemical compound O=C1CCCCC1=C1CCCCC1 TYDSIOSLHQWFOU-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001546 nitrifying effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 241001575025 Larisa Species 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 102000005877 Peptide Initiation Factors Human genes 0.000 description 1
- 108010044843 Peptide Initiation Factors Proteins 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
- B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
-
- 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
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00092—Tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00186—Controlling or regulating processes controlling the composition of the reactive mixture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00245—Avoiding undesirable reactions or side-effects
- B01J2219/00259—Preventing runaway of the chemical reaction
- B01J2219/00263—Preventing explosion of the chemical mixture
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a device and a method for producing cyclic ketone by oxidizing cyclic olefin with nitrous oxide, wherein the device comprises a nitrogen tank, a cyclic olefin metering tank, a nitrous oxide metering tank, a heat exchanger, a preheater, a fixed bed reactor, a cooler, a high-pressure separator, a cryogenic gas discharge tank and a low-pressure separator. Adding an inert porous material into the fixed bed reactor, continuously introducing cycloolefin or a mixture of cycloolefin and saturated alkane and nitrous oxide into the fixed bed reactor through a heat exchanger, exchanging heat with the reaction raw materials through the heat exchanger, cooling through a cooler to separate gas from liquid, allowing a liquid phase part to enter a low-pressure separator to separate residual gas again, and separating a liquid part product from the low-pressure separator. The equipment is convenient to assemble, the method is simple, the inert porous material is effectively utilized, and cyclic olefin and nitrous oxide can react at a mol ratio higher than the common upper explosion limit to generate cyclic ketone compounds.
Description
Technical Field
The invention belongs to the field of chemical manufacturing, and relates to equipment and a method for producing cyclic ketone by oxidizing cyclic olefin with nitrous oxide.
Background
In environmental science research, in particular in the field of global climate change, N 2 O, commonly referred to as nitrous oxide, is a greenhouse gas, has a greenhouse effect, contributes to global warming, and is one of 6 greenhouse gases specified in the kyoto protocol. N (N) 2 The O has long residence time in the atmosphere and can be transported to stratosphere, resulting in ozone layer destruction, ozone cavitation, and human beingsAnd other organisms exposed to solar ultraviolet radiation, can cause damage to the human skin, eyes, and immune system.
Although N is compared with carbon dioxide 2 O is very low in the atmosphere, belongs to trace gases but has a single molecule warming potential 298 times that of carbon dioxide (IPCC, 2007); the effect on global gas warming will be more and more remarkable in the future, N 2 The increase in O concentration has attracted considerable attention from scientists. Research on this problem is being conducted in depth.
Atmosphere N 2 One of the important sources of O is the farmland ecosystem. In the soil, N 2 O is produced by nitrifying and denitrifying microorganisms, and people apply excessive nitrogen fertilizer into farmlands to promote microbial activity, and nitrogen is converted into N through the nitrifying and denitrifying processes 2 O. The biological denitrification and denitrification process of sewage can also cause the discharge of nitrous oxide, and the limitation of dissolved oxygen, the accumulation of nitrite and the oxidation of hydroxylamine are all causes of nitrous oxide.
Design capacity of adipic acid production device of China Petroleum Liaoyang petrochemical industry limited company and annual byproduct N 2 About 5 ten thousand tons of O, conventional N used 2 The O emission reduction device adopts the catalytic decomposition technology of German Basf company, introduces a new device of German Shi Daole (STEULE) company process package, and aims to reduce inert greenhouse gas N 2 O is discharged. About 5330kg of N is produced per hour during the production of adipic acid 2 O gas, via N 2 After the O emission reduction device is treated, more than 95% of N 2 O is decomposed into N 2 And O 2 . Traditional N 2 The O emission reduction device is built in 8 months of 2007, mainly comprises N 2 O emission reduction reaction unit, NO 2 The device comprises an emission reduction reaction unit, a waste heat recovery unit, an air compressor unit and the like. Traditional N 2 O emission reduction device is built into production in 2008 3 months, and N is reduced in annual design 2 The O gas is 4.1 ten thousand tons, and the design start time is 8000 hours/year.
Generating N by adopting a decomposition method 2 Gas and O 2 The gas is discharged into the atmosphere, and the domestic adipic acid production device produces a byproduct N every year 2 O is about 100 ten thousand tons.
Chinese patent publication No.: CN104761438A, filed as basf european company, process for the preparation of cyclic ketones. The cyclic ketone compound is generated by the reaction of nitrous oxide and cycloolefin, and the cyclic ketone production equipment is built in Europe by utilizing the theory of Pasteur for the oxidation of cycloolefin, so that the cyclic ketone production equipment is put into production.
U.S. patent publication No.: US20060106258A1, filed by PANOV GENNADY I, DUBKOV KONSTANTIN A, STAROKON EVGENY V, PIRUTKO LARISA V, METHOD FOR PRODUCING MONOCYCLIC KETONES C 4 -C 5 The concentration of nitrous oxide in the reaction with cycloolefins in an inert gas to form cyclic ketone compounds is indicated to be not more than 25%, otherwise explosions occur.
Chinese patent publication No.: CN104761438A, filed as basf european company, process for the preparation of cyclic ketones. The molar ratio of the nitrous oxide to the cycloolefin to the cyclic ketone compound is limited to 0.02 to 0.3, preferably 0.05 to 0.25, and is controlled below the explosion range.
The reaction of cycloolefin with nitrous oxide in the liquid phase is a well known theory, which requires a reaction at high temperature to meet the requirement of having sufficient reaction activation energy, but at high temperature, a large amount of cycloolefin exists in the gas phase, so that the collision probability of cycloolefin with nitrous oxide is reduced, and the reaction is difficult to be carried out.
Disclosure of Invention
Object of the Invention
In order to solve the problems of the reaction of cycloolefin and nitrous oxide in the prior art, the present invention provides an apparatus and a method for producing cyclic ketone by oxidizing cycloolefin with nitrous oxide.
Technical proposal
The equipment for producing cyclic ketone by oxidizing cycloolefin with nitrous oxide comprises a nitrogen tank, a cycloolefin metering tank, a nitrous oxide metering tank, a heat exchanger, a preheater, a fixed bed reactor, a cooler, a high-pressure separator, a cryogenic gas discharge tank and a low-pressure separator, wherein the cycloolefin metering tank is provided with a cycloolefin inlet, an outlet of the cycloolefin metering tank is connected with an inlet of the fixed bed reactor through a pipeline through the heat exchanger and the preheater, the nitrous oxide metering tank is provided with a nitrous oxide inlet, an outlet of the nitrous oxide metering tank is connected with an inlet of the fixed bed reactor through a pipeline through the heat exchanger and the preheater, an outlet of the fixed bed reactor is connected with an inlet of the high-pressure separator through a pipeline through the heat exchanger and the cooler, an outlet of the upper end of the high-pressure separator is connected with an inlet of the cryogenic gas discharge tank through a pipeline, an outlet of the lower end of the cryogenic gas discharge tank is provided with a product collecting port, and an upper end of the low-pressure separator is provided with a gas discharge port; the cycloolefin metering tank, the nitrous oxide metering tank, the heat exchanger, the preheater, the fixed bed reactor, the cooler, the high-pressure separator, the cryogenic gas discharge tank and the low-pressure separator are all connected with a nitrogen tank through pipelines, and the nitrogen tank is provided with a nitrogen inlet.
Further, the bottom ends of the cycloolefin metering tank, the nitrous oxide metering tank, the heat exchanger, the preheater, the fixed bed reactor, the cooler, the high-pressure separator, the cryogenic gas discharge tank and the low-pressure separator are provided with low discharge ports.
Furthermore, a cycloolefin metering booster pump is arranged on an outlet pipeline of the cycloolefin metering tank, a nitrous oxide metering booster pump is arranged on an outlet pipeline of the nitrous oxide metering tank, a filter is arranged on an outlet pipeline of the fixed bed reactor, and an inlet pipeline of the fixed bed reactor is also connected with the nitrogen tank.
A method for producing cyclic ketone by using equipment and oxidizing cycloolefin with nitrous oxide comprises the steps of adding an inert porous material into a fixed bed reactor, continuously introducing cycloolefin or a mixture of cycloolefin and saturated alkane and nitrous oxide into the fixed bed reactor through a heat exchanger and a preheater at a reaction temperature of 100-350 ℃ and a reaction pressure of 5-30 MPa, wherein the mol ratio of cycloolefin to nitrous oxide is 1:0.05-1:0.9, and carrying out the following reaction:
C n H 2n-2 +N 2 O→C n H 2n-2 O+N 2 ↑
wherein: n is a positive integer of 4 to 20;
cyclic ketones as reaction productsAnd unreacted starting materials and N produced 2 The reaction product is cooled to 0-35 ℃ by a cooler after heat exchange with the reaction raw materials, gas-liquid phase separation is carried out by a high-pressure separator, the liquid phase part enters a low-pressure separator to be separated into residual gas again, and the gas part separated by the low-pressure separator is N 2 The gas is discharged, and the liquid part product separated by the low-pressure separator contains cyclic ketone C n H 2n-2 Separating out liquid part product containing cyclic ketone from low pressure separator, rectifying, detecting cyclic ketone product by color-mass spectrum and chromatographic analysis, recycling light cyclic olefin and saturated alkane, condensing gas phase component in high pressure separator in deep cold gas discharge tank at-10-10deg.C, separating, recovering and recycling by condensing liquid part rectifying device, and separating by-product N in deep cold gas discharge tank 2 And (5) discharging gas.
Further, after the inert porous material is added into the fixed bed reactor, N in a nitrogen tank is needed before the reaction starts 2 The whole equipment is purged by gas, and the gas is expressed as N 2 The subsequent reaction is carried out under the protection of gas, after the mixture of cycloolefin or cycloolefin and saturated alkane and nitrous oxide pass through a heat exchanger, the temperature reaches 100-200 ℃, after the mixture passes through a preheater, the temperature reaches 210-350 ℃, the reaction temperature in a fixed bed reactor is controlled, the reaction is carried out under the condition of 100-350 ℃, the pressure in the fixed bed reactor works at 5-30 MPa, and the materials entering a cooler are cooled to 0-35 ℃ by the cooler.
Further, a cage type heat exchanger is arranged in the fixed bed reactor, and the model of the cage type heat exchanger is Chinese patent publication number: CN209197530U, patent name: a cage heat exchanger in the catalytic hydrogenation reactor is filled with a heat carrier at 100-350 ℃ for removing heat released in the reaction process of cycloolefin and nitrous oxide, an inert porous material is added into the inner cavity of the fixed bed reactor, the fixed bed reactor is a tubular fixed bed reactor, a jacket layer is arranged outside the tubular fixed reactor, the heat carrier at 100-350 ℃ is filled in the jacket, and the heat carrier removes the heat released in the reaction process of cycloolefin and nitrous oxide; the tube type fixed bed reactor is a single tube or multi-tube parallel fixed bed reactor.
Further, the inert porous material is one or more of porous ceramics, porous glass or porous aluminum oxide, the structure of the inert porous material is cylindrical or spherical, the size of the cylindrical is phi 5mm multiplied by 5mm to phi 20mm multiplied by 20mm, the radius R of the spherical is 5mm to 20mm, and the inert porous material has a specific surface area of 30 to 260m 2 Per g, pore diameter 5-300 nm, positive pressure intensity >150kgf/cm 2 。
Further, the inert porous material has a specific surface area of 30-170 m 2 And/g, pore diameter is 5-230 nm.
Further, the cycloolefin is C 4 ～C 2O Monocyclomonoolefins of the formula C n H 2n-2 Wherein n=a positive integer from 4 to 20; the cycloolefin may be pure cycloolefin or a mixture containing saturated alkane in cycloolefin, and when the cycloolefin is a mixture containing saturated alkane in cycloolefin, the mol ratio of cycloolefin to saturated alkane is 1: 1-1: 30, the saturated alkane may be C 4 ～C 2O Mono-, linear-or branched-chain alkanes.
Further, the fixed bed reactor is a vertical reactor, the mixture of cycloolefin or cycloolefin and saturated alkane is injected from the top of the fixed bed reactor at one time, the nitrous oxide is injected from the top of the fixed bed reactor at one time, or the nitrous oxide is injected into the fixed bed reactor from the top, middle and lower 3 positions of the fixed bed reactor in three parts, wherein the top feeding position is 0.0% -20% of the top of the fixed bed reactor from top to bottom, the middle feeding position is 20% -40% of the top of the fixed bed reactor from top to bottom, the lower feeding position is 40% -70% of the top of the fixed bed reactor from top to bottom, and the proportion of the fed nitrous oxide in the three parts is 20% -40% of the total feeding amount of the nitrous oxide. Or nitrous oxide is injected uniformly from 0.0% to 70% of the top of the fixed bed reactor (K101).
Advantages and effects
Firstly, the equipment is convenient to assemble, the method is simple, and the inert porous material is effectively utilized. The inert porous material has the characteristic of large specific surface area, firstly raw materials of cycloolefin and nitrous oxide enter a fixed bed reactor, then quickly enter the pores of the inert porous material and are adsorbed on the inner surface layer of the porous material, so that the nitrous oxide and the cycloolefin react in the pores to generate the cyclic ketone compound. The large specific surface area in the pores of the inert porous material reduces the generated explosion initiation factors, free radicals collide and deactivate on the surface of the porous material, and the sources of the explosion factors are eliminated; secondly, chinese patent publication number: CN209197530U, patent name: the cage heat exchanger in the catalytic hydrogenation reactor removes heat released by the reaction in time, reduces the temperature of a reaction hot spot, and reduces the rate of free radical generation and the risk of explosion under the condition that the reaction is close to a controllable constant temperature interval.
In combination with the above two advantages, cycloolefins can be reacted with nitrous oxide to form cyclic ketone compounds in a molar ratio above the usual upper explosion limit.
Drawings
The invention is further described below with reference to the drawings and the detailed description. The scope of the present invention is not limited to the following description.
FIG. 1 is a schematic diagram showing the connection structure of an apparatus for producing cyclic ketones by oxidizing cyclic olefins with nitrous oxide;
FIG. 2 is a general conventional fixed bed hydrogenation reactor;
FIG. 3 is a block diagram of a cage heat exchanger;
FIG. 4 is a diagram of an inner ring support ring structure;
FIG. 5 shows a ring support ring construction;
FIG. 6 outer race support ring construction;
FIG. 7 is a schematic top view of a cage heat exchanger superstructure;
FIG. 8 is a schematic diagram of the connection structure of the support ring and the heat exchanger tube array.
Reference numerals illustrate: E101. heat exchanger, e102, preheater, f101, filter, k101, fixed bed reactor, p101, cyclic olefin metering booster pump, p102, nitrous oxide metering booster pump, r101, cyclic olefin metering tank, r102, nitrous oxide metering tank, r103, cooler, r104, high pressure separator, r105, deep cold gas discharge tank, r106, low pressure separator, v101, nitrogen tank, 1, heat carrier inlet conduit, 2, heat carrier distribution conduit, 3, heat carrier distribution conduit, 4, inner ring heat exchanger train, 5, middle ring heat exchanger train, 6, outer ring heat exchanger train, 7, inner ring support ring, 8, middle ring support ring, 9, outer ring support ring, 10, heat carrier header, 11, 12, heat carrier header, 13, heat carrier outlet conduit, 14, vent, 15, inner ring heat exchanger train support ring, 16, middle ring heat exchanger train support ring cavity, 17, outer ring support ring cavity, 19.
Detailed Description
As shown in fig. 1, L represents a level gauge, T represents a temperature transmitter, and P represents a pressure transmitter. An apparatus for producing cyclic ketone by oxidizing cyclic olefin with nitrous oxide comprises a nitrogen tank V101, a cyclic olefin metering tank R101, a nitrous oxide metering tank R102, a heat exchanger E101, a preheater E102, a fixed bed reactor K101, a cooler R103, a high-pressure separator R104, a cryogenic gas discharge tank R105 and a low-pressure separator R106, wherein the cyclic olefin metering tank R101 is provided with a cyclic olefin inlet, the outlet of the cyclic olefin metering tank R101 is connected with the inlet of the fixed bed reactor K101 through a pipeline through the heat exchanger E101 and the preheater E102, the nitrous oxide metering tank R102 is provided with a nitrous oxide inlet, the outlet of the nitrous oxide metering tank R102 is connected with the inlet of the fixed bed reactor K101 through the heat exchanger E101 and the preheater E102, the outlet of the fixed bed reactor K101 is connected with the inlet of the high-pressure separator R104 through the pipeline through the heat exchanger E101 and the cooler R103, the outlet at the upper end of the high-pressure separator R104 is connected with the inlet of the cryogenic gas discharge tank R105 through the pipeline, the upper end of the cryogenic gas discharge tank R105 is provided with a nitrogen discharge outlet at the upper end of the cryogenic gas discharge tank R105, the low-pressure separator R106 is provided with a low-pressure separator R106 at the lower end of the low-pressure separator R106 is provided with a product outlet at the inlet of the low-pressure separator; the cycloolefin metering tank R101, the nitrous oxide metering tank R102, the heat exchanger E101, the preheater E102, the fixed bed reactor K101, the cooler R103, the high-pressure separator R104, the cryogenic gas discharge tank R105 and the low-pressure separator R106 are all connected with the nitrogen tank V101 through pipelines, and the nitrogen tank V101 is provided with a nitrogen inlet.
The bottom ends of the cycloolefin metering tank R101, the nitrous oxide metering tank R102, the heat exchanger E101, the preheater E102, the fixed bed reactor K101, the cooler R103, the high-pressure separator R104, the cryogenic gas discharge tank R105 and the low-pressure separator R106 are provided with low-discharge ports.
The outlet pipe of the cycloolefin metering tank R101 is provided with a cycloolefin metering booster pump P101, the outlet pipe of the nitrous oxide metering tank R102 is provided with a nitrous oxide metering booster pump P102, the outlet pipe of the fixed bed reactor K101 is provided with a filter F101, and the inlet pipe of the fixed bed reactor K101 is also connected with a nitrogen tank V101.
A method for preparing cyclic ketone by oxidizing cyclic olefin with nitrous oxide comprises adding inert porous material into fixed bed reactor K101, and using N of nitrogen tank V101 2 Air purging the entire apparatus, detecting the discharge N of each of the "can" and "machine 2 The next reaction can be carried out when the oxygen content is less than 0.1 ppm. At N 2 The subsequent reaction is carried out under the protection of gas,
under the conditions of the reaction temperature of 100-350 ℃ and the reaction pressure of 5-30 MPa, the temperature of the cycloolefin or the mixture of the cycloolefin and the saturated alkane and the nitrous oxide are respectively and continuously introduced into a fixed bed reactor K101 through a heat exchanger E101 to reach 100-200 ℃ and a preheater E102 to reach 210-350 ℃, the nitrous oxide raw material preferably uses high-purity nitrous oxide liquid, the nitrous oxide purity is more than 99.5%, the mol ratio of the cycloolefin to the nitrous oxide is 1:0.05-1:0.9, and the following reactions occur:
C n H 2n-2 cycloolefin+N 2 O nitrous oxide → C n H 2n-2 O product cyclic ketone +N 2 ≡nitrogen
Wherein: n is a positive integer of 4 to 20;
the conversion rate of the nitrous oxide reaches 100%, the single conversion rate of the cycloolefin is 56% -87%, the selectivity of the single-formed cycloolefin to the corresponding cyclic ketone is more than or equal to 98%, and the nitrous oxide enters the fixed bed reactor in a way that the nitrous oxide enters the reactor from the top of the fixed bed reactor K101 and the cycloolefin or the mixture of the cycloolefin and the saturated alkane simultaneously enter the reactor; reaction product cyclic ketone and unreacted starting material and N produced 2 Heat exchange is carried out between the heat exchanger E101 and the reaction raw materials, the heat released by the reaction is circularly removed by the heat carrier of the heat exchanger in the fixed bed reactor K101 to ensure that the reaction keeps constant temperature, the heat released by the reaction can be also removed by the heat carrier circulated in the jacket of the tubular fixed bed reactor, the reaction temperature in the fixed bed reactor K101 is controlled to be 100-350 ℃, the reaction is carried out under the condition of preferably 220-330 ℃, the pressure in the fixed bed reactor K101 is operated at 5-30 MPa, preferably 8.0-25 MPa, the reaction product is cooled to 0-35 ℃ by a cooler R103, gas-liquid phase separation is carried out by a high-pressure separator R104, the liquid phase part enters a low-pressure separator R106 to separate residual gas again, and the gas part separated by the low-pressure separator R106 is N 2 The nitrous oxide content in the detected gas is less than 1ppm, namely the gas is discharged after being qualified, and the liquid part product separated by the low-pressure separator R106 contains cyclic ketone C n H 2n-2 Separating out the liquid part product of R106 containing cyclic ketone from the low-pressure separator, rectifying the cyclic ketone product, detecting the cyclic ketone product by chromatography analysis through color-mass spectrometry, recycling the light-component cyclic olefin and saturated alkane obtained by rectifying, condensing the gas phase component in the high-pressure separator R104 at-10 ℃ in the deep cold gas discharge tank R105 through the high-pressure separator R104, separating, recycling and recycling the liquid part rectification device obtained by condensing, and separating the byproduct N from the deep cold gas discharge tank R105 2 And (3) detecting that the nitrous oxide content in the gas is less than 1ppm, and discharging after the nitrous oxide content is qualified.
The inside of the fixed bed reactor K101 is provided with a cage type heat exchanger, and the model of the cage type heat exchanger is Chinese patent publication number: CN209197530U, patent name: a cage type heat exchanger in a catalytic hydrogenation reactor has the following specific structure: comprises a heat carrier inlet conduit 1, a heat carrier distribution conduit 2, a heat carrier distribution conduit box 3, a heat exchanger tube array, a support ring, a heat carrier collection conduit box 10, a spiral tube 11, a heat carrier collection conduit 12 and a heat carrier outlet conduit 13; the heat carrier inlet conduit 1 is positioned at the uppermost end of the heat exchanger, the heat carrier inlet conduit 1 is connected with a heat carrier distribution pipe 2, the heat carrier distribution pipe 2 is connected with a heat carrier distribution pipe box 3, the heat carrier distribution pipe box 3 is in a ring shape, the heat carrier distribution pipe box 3 is connected with a plurality of groups of concentric heat exchanger tubes which are uniformly distributed circumferentially, the heat exchanger tubes are supported by a plurality of layers of supporting rings, the lower ends of the heat exchanger tubes are connected with a heat carrier collecting pipe box 10, the lower side of the heat carrier collecting pipe box 10 is connected with a plurality of groups of spiral pipes 11 which are coiled together, the lower end of each spiral pipe 11 is connected with a heat carrier collecting pipe 12, and the other end of each heat carrier collecting pipe 12 is connected with a heat carrier outlet conduit 13 at the lowermost end of the heat exchanger; the heat exchanger tube array comprises an inner ring heat exchanger tube array 4, a middle ring heat exchanger tube array 5 and an outer ring heat exchanger tube array 6, and the support rings comprise an inner ring support ring 7, a middle ring support ring 8 and an outer ring support ring 9; the inner ring support ring 7 is provided with ventilation holes 14, the outer ring of the inner ring support ring 7 is provided with inner ring heat exchanger tube array support grooves 15 which are uniformly distributed and have the same number as the inner ring heat exchanger tube arrays 4, and the inner ring heat exchanger tube array support grooves 15 are welded with the inner ring heat exchanger tube arrays 4; the middle ring support ring 8 is provided with a middle ring support ring inner cavity 16, the diameter of the middle ring support ring inner cavity 16 is larger than the outer diameter of the inner ring support ring 7, the outer ring of the middle ring support ring 8 is provided with middle ring heat exchanger tube array support grooves 17 which are uniformly distributed and the same as the number of the middle ring heat exchanger tubes 5, and the middle ring heat exchanger tube array support grooves 17 and the middle ring heat exchanger tubes 5 are welded together; the outer ring support ring 9 is provided with an outer ring support ring inner cavity 18, the diameter of the outer ring support ring inner cavity 18 is larger than the outer diameter of the middle ring support ring 8, the outer ring of the outer ring support ring 9 is provided with outer ring heat exchanger tube array support grooves 19 which are uniformly distributed and have the same number as the outer ring heat exchanger tube arrays 6, and the outer ring heat exchanger tube array support grooves 19 are welded with the outer ring heat exchanger tube arrays 6; the heat carrier at 100-350 ℃ is introduced into a cage heat exchanger in the catalytic hydrogenation reactor and is used for removing heat released in the reaction process of cycloolefin and nitrous oxide, an inert porous material is added into an inner cavity of the fixed bed reactor, the fixed bed reactor is a tubular fixed bed reactor, a jacket layer is arranged outside the tubular fixed reactor, and the heat released in the reaction process of cycloolefin and nitrous oxide is removed by the heat carrier at 100-350 ℃ in the jacket; the tube type fixed bed reactor is a single tube or multi-tube parallel fixed bed reactor.
The inert porous material is one or more of porous ceramic, porous glass or porous aluminum oxide, the structure of the inert porous material is cylindrical or spherical, the size of the cylindrical is phi 5mm multiplied by 5 mm-phi 20mm multiplied by 20mm, the radius R of the spherical is 5 mm-20 mm, and the inert porous material has a specific surface area of 30-260 m 2 Per g, pore diameter 5-300 nm, positive pressure intensity>150kgf/cm 2 . The inert porous material has a specific surface area of 30-170 m 2 And/g, pore diameter is 5-230 nm.
Cycloolefin is C 4 ～C 2O Monocyclomonoolefins of the formula C n H 2n-2 Wherein n=a positive integer from 4 to 20; the cycloolefin may be pure cycloolefin or a mixture containing saturated alkane in cycloolefin, and when the cycloolefin is a mixture containing saturated alkane in cycloolefin, the mol ratio of cycloolefin to saturated alkane is 1: 1-1: 30, the saturated alkane may be C 4 ～C 2O Mono-, linear-or branched-chain alkanes.
The fixed bed reactor K101 is a vertical reactor, cycloolefin or a mixture of cycloolefin and saturated alkane is injected from the top of the fixed bed reactor K101 at one time, nitrous oxide is injected from the top of the fixed bed reactor K101 at one time, or nitrous oxide is injected into the fixed bed reactor K101 in three parts from 3 positions of the top, the middle and the lower part of the fixed bed reactor K101, the top feeding position refers to the position of 0.0% -20% from top to bottom of the fixed bed reactor K101, the middle feeding position refers to the position of 20% -40% from top to bottom of the fixed bed reactor K101, the lower feeding position refers to the position of 40% -70% from top of the fixed bed reactor K101, the proportion of the fed amount of nitrous oxide respectively accounts for 20% -40% of the total amount of nitrous oxide, or the feeding position of 0.0% -70% of the fed amount of nitrous oxide from the top of the fixed bed reactor (K101) is uniformly injected.
Example 1
The length of the fixed bed reactor is 6m, the inner diameter DN300 (the diameter is 300 mm) of the fixed bed reactor is internally provided with a cage heat exchanger of CN209197530U patent, the fixed bed reactor is internally filled with inert porous aluminum oxide filler with phi 5mm multiplied by 5mm in length, and the inert porous material has specific surface area of 30-120 m 2 Per gram, pore diameter of 5-20 nm, positive pressure of 170kgf/cm 2 . The fixed bed reactor is externally provided with an asbestos heat preservation layer, the content of nitrous oxide liquid serving as a raw material is more than 99.5%, the content of cyclopentene serving as a raw material is more than or equal to 99.8%, and cyclopentene is prepared into a mixture of cyclopentene, cyclopentane and cyclohexane according to the proportion: cyclopentane: cyclohexane=1:1:6 (mol ratio), mol ratio of cyclopentene to nitrous oxide of 1:0.6, space velocity of 100mol/h (in mol of cyclopentene per hour at inlet of fixed bed reactor), and apparatus shown in fig. 1 was used with N 2 3 times of gas displacement, wherein the oxygen content of the gas in the detection device is less than 0.1PPm, the heat carrier flowing through a cage type heat exchanger of a fixed bed reactor K101 is preheated to 260+/-5 ℃, and the temperature is controlled according to cyclopentene: cyclopentane: the mixture of solvent reactants and nitrous oxide with cyclohexane=1:1:6 (mol ratio) are respectively fed into a heat exchanger E101 by a plunger pump, heat exchange is carried out on the mixture and nitrous oxide with products from the outlet of a fixed bed reactor K101, the mixture and nitrous oxide are fed into a preheater E102 for preheating to 270+/-5 ℃ after heat exchange, the mixture of solvent reactants and nitrous oxide with 270+/-5 ℃ respectively enter the fixed bed reactor from the top of the fixed bed reactor K101, the temperature and the flow of a heat carrier in the cage type heat exchanger are used for regulating the temperature of a bed layer in the fixed bed reactor to be within a range of 285+/-20 ℃, meanwhile, the pressure in the fixed bed reactor is controlled to be 18MPa by a regulating valve, so that cyclopentene and nitrous oxide fully react, a hot spot temperature zone is generated in the reactor bed layer (a range of 1m to 2.5m from a feed inlet, and the highest hot spot temperature 317 DEG), and the mixture generated in the reaction enters the heat exchanger E101 through a discharge port at the bottom of the fixed bed reactor K101, and the reaction after heat exchange is carried out by the heat exchanger E101 The mixture enters a cooler R103 to be cooled to 20+/-3 ℃, and the cooled liquid is N 2 The mixture enters a high-pressure separator R104 through the control of a regulating valve to carry out gas-liquid phase separation, the liquid part of the high-pressure separator R104 enters a low-pressure separator R106 through the control of the regulating valve, the pressure of the low-pressure separator is regulated to 0.1MPa through the regulating valve, a sampling point A is arranged on the liquid part in the low-pressure separator R106, the liquid part is subjected to qualitative analysis by using a color-mass spectrum, the liquid composition is determined to contain raw materials of cyclopentane, cyclohexane and unreacted cyclopentene through the qualitative analysis, and new color-mass spectrum peaks are generated to be qualitatively classified into cyclopentanone and 2-cyclopentylene cyclopentanone. The conversion of cyclopentene into the single product was 59.1% (the theoretical consumption of cyclopentene should be 60mol, and the actual consumption of 59.1mol, if the consumption of cyclopentene was equal to the mol of nitrous oxide, based on the amount of dinitrogen monoxide charged), the amount of the desired product cyclopentanone to be produced was 57.92mol, the desired product cyclopentanone selectivity was 98.2%, and the selectivity of the by-product 2-cyclopentylene was 0.6% based on the amount of 59.1mol/h cyclopentene to be consumed.
The gas part separated by the low-pressure separator R106 is provided with a sampling port B, and the sampling contains N through gas-mass spectrometry qualitative analysis 2 The gas mass content is more than 99.5%, no nitrous oxide is detected, and the gas part separated by the low pressure separator R106 contains trace amounts of cyclopentane, cyclohexane and cyclopentene and N by gas chromatography quantitative analysis 2 The gas volume ratio is less than 0.5%. The gas part separated by the high-pressure separator R104 is controlled and regulated to 0.1MPa by a regulating valve F106, enters a deep-cooling gas discharge tank R105, is cooled to-5 to-10 ℃, a sampling point C is arranged on the liquid part of the deep-cooling gas discharge tank R105, a trace amount of organic liquid is contained in condensate, the gas part of the deep-cooling gas discharge tank R105 is provided with a sampling point D after being analyzed to contain cyclopentane, cyclohexane and cyclopentene, and the main component of the sample is N after being qualitatively analyzed by a color-mass spectrum 2 The gas contains no nitrous oxide, and contains trace amounts of cyclopentane, cyclohexane and cyclopentene, and the main composition of the quantitative chromatographic detection comprises N 2 The gas has a mass content of more than 99.5% and contains less than 0.5% of a mixture of cyclohexane, cyclopentane and cyclopentene.
The nitrous oxide is completely converted during the reaction.
The low-pressure separator R106 and the deep-cooling gas discharge tank R105 are recycled through pressure swing adsorption of organic matters, and are discharged after the nitrogen is detected to be qualified, and the liquid part of the deep-cooling gas discharge tank R105 is recycled.
Example 2
The length of the fixed bed reactor is 6m, the inner diameter DN300 of the fixed bed reactor is provided with a cage type heat exchanger of CN209197530U patent, the fixed bed reactor is filled with inert porous aluminum oxide filler with phi 5mm multiplied by 5mm, and the inert porous material has specific surface area of 30-120 m 2 Per gram, pore diameter of 5-20 nm, positive pressure of 170kgf/cm 2 . The fixed bed reactor is externally provided with an asbestos heat preservation layer, the content of nitrous oxide liquid serving as a raw material is more than 99.5%, the content of cyclopentene serving as a raw material is more than or equal to 99.8%, and cyclopentene is prepared into a mixture of cyclopentene, cyclopentane and cyclohexane according to the proportion: cyclopentane: cyclohexane=1:1:7 (mol ratio), mol ratio of cyclopentene to nitrous oxide is 1:0.8, space velocity 100mol/h (in mol of cyclopentene per hour at the inlet of the fixed bed reactor). N for devices shown in the process flow diagram 2 3 times of gas displacement, wherein the oxygen content of the gas in the detection device is less than 0.1PPm, the heat carrier flowing through a cage type heat exchanger of a fixed bed reactor K101 is preheated to 260+/-5 ℃, and the temperature is controlled according to cyclopentene: cyclopentane: the mixture of solvent reactants and nitrous oxide with cyclohexane=1:1:7 (mol ratio) are respectively fed into a heat exchanger E101 by a plunger pump, heat exchange is carried out on the mixture and the product from the outlet of a fixed bed reactor K101, the mixture enters a preheater E102 for preheating to 270+/-5 ℃ after heat exchange, the mixture of solvent reactants and nitrous oxide with 270+/-5 ℃ respectively enter the fixed bed reactor from the top of the fixed bed reactor K101, the temperature and the flow of a heat carrier in the cage type heat exchanger are used for regulating the temperature of the bed layer in the fixed bed reactor to be in a range of 295+/-20 ℃, meanwhile, the pressure in the fixed bed reactor is controlled to be 19MPa by a regulating valve, the cyclopentene and the nitrous oxide are fully reacted, a hot spot temperature zone is generated in the reactor bed layer (in a range of 1m to 2.0m from a feed inlet, the highest hot spot temperature is 336 ℃, the mixture generated in the reaction enters the heat exchanger E101 from a discharge port at the bottom of the fixed bed reactor K101, and the reaction mixture after heat exchange of the heat exchanger E101 enters a cooler R103 for cooling To 20+/-3 ℃, and the cooled liquid is N 2 The mixture enters a high-pressure separator R104 through the control of a regulating valve to carry out gas-liquid phase separation, the liquid part of the high-pressure separator R104 enters a low-pressure separator R106 through the control of the regulating valve, the pressure of the low-pressure separator is regulated to 0.1MPa through the regulating valve, a sampling point A is arranged on the liquid part in the low-pressure separator R106, the liquid part is subjected to qualitative analysis by using a color-mass spectrum, the liquid composition is determined to contain raw materials of cyclopentane, cyclohexane and unreacted cyclopentene through the qualitative analysis, and new color-mass spectrum peaks are generated to be qualitatively classified into cyclopentanone and 2-cyclopentylene cyclopentanone. The conversion of cyclopentene was found to be 76% (80 mol, in theory, 76mol, should be consumed if equal mol of cyclopentene was consumed by the reaction based on the mol of nitrous oxide charged), 98.6% of the desired product cyclopentanone was produced based on 76mol/h of cyclopentene consumed, and 0.5% of the by-product 2-cyclopentylene was produced.
The gas part separated by the low-pressure separator R106 is provided with a sampling port B, and the sampling contains N through gas-mass spectrometry qualitative analysis 2 The gas mass content is more than 99.5%, no nitrous oxide is detected, and the gas part separated by the low pressure separator R106 contains trace amounts of cyclopentane, cyclohexane and cyclopentene and N by gas chromatography quantitative analysis 2 The gas volume ratio is less than 0.5%. The gas part separated by the high-pressure separator R104 is controlled and regulated to 0.1MPa by a regulating valve F106, enters a deep-cooling gas discharge tank R105, is cooled to-5 to-10 ℃, a sampling point C is arranged on the liquid part of the deep-cooling gas discharge tank R105, a trace amount of organic liquid is contained in condensate, the gas part of the deep-cooling gas discharge tank R105 is provided with a sampling point D after being analyzed to contain cyclopentane, cyclohexane and cyclopentene, and the main component of the sample is N after being qualitatively analyzed by a color-mass spectrum 2 The gas contains no nitrous oxide, and contains trace amounts of cyclopentane, cyclohexane and cyclopentene, and the main composition of the quantitative chromatographic detection comprises N 2 The gas has a mass content of more than 99.5% and contains less than 0.5% of a mixture of cyclohexane, cyclopentane and cyclopentene.
The nitrous oxide is completely converted during the reaction.
The low-pressure separator and the gas part of the deep-cooling gas discharge tank R105 are recycled through pressure swing adsorption of organic matters, and are discharged after the nitrogen is detected to be qualified, and the liquid part of the deep-cooling gas discharge tank R105 is recycled.
Example 3
The length of the fixed bed reactor is 6m, the inner diameter DN300 of the fixed bed reactor is provided with a cage type heat exchanger of CN209197530U patent, the fixed bed reactor is filled with inert porous aluminum oxide filler with phi 5mm multiplied by 5mm, and the inert porous material has specific surface area of 30-120 m 2 Per gram, pore diameter of 5-20 nm, positive pressure of 170kgf/cm 2 . The fixed bed reactor is externally provided with an asbestos heat preservation layer, the content of nitrous oxide liquid serving as a raw material is more than 99.5%, the content of cyclopentene serving as a raw material is more than or equal to 99.8%, and cyclopentene is prepared into a mixture of cyclopentene, cyclopentane and cyclohexane according to the proportion: cyclopentane: cyclohexane=1:1:9 (molar ratio), molar ratio of cyclopentene to nitrous oxide of 1:0.9, space velocity 100mol/h (in mol of cyclopentene per hour entering the fixed bed reactor). N for devices shown in the process flow diagram 2 3 times of gas displacement, wherein the oxygen content of the gas in the detection device is less than 0.1PPm, and the heat carrier flowing through a cage type heat exchanger of a fixed bed reactor K101 is preheated to 290+/-5 ℃ according to cyclopentene: cyclopentane: cyclohexane=1:1:9 (mol ratio) solvent reactant mixture enters a heat exchanger E101 by a plunger pump, exchanges heat with a product from an outlet of a fixed bed reactor K101, enters a preheater E102 for preheating to 290+/-5 ℃ after exchanging heat, the solvent reactant mixture reaching 290+/-5 ℃ enters the fixed bed reactor K101 from the top of the fixed bed reactor at one time, nitrous oxide enters the heat exchanger E101 by the plunger pump, exchanges heat with the product from the outlet of the fixed bed reactor K101, enters the preheater E102 for preheating to 290+/-5 ℃ after exchanging heat, the nitrous oxide reaching 290+/-5 ℃ enters the fixed bed reactor K101 from the top, the middle part and the lower part, the top feeding position refers to the position of 0.0% from top to bottom of the fixed bed reactor K101, the middle feeding position refers to the position of 30% from top to bottom of the fixed bed reactor K101, the lower feeding position refers to the position of 60% from top to bottom of the fixed bed reactor K101, the total nitrous oxide content of one part of three nitrous oxide feed amounts respectively accounts for 33%, 34%,33%, regulating the temperature of a heat carrier in a cage type heat exchanger and the flow rate to be within 295+/-20 ℃, controlling the pressure in the fixed bed reactor to be 15MPa by a regulating valve, fully reacting cyclopentene with nitrous oxide, generating stable hot spot temperature region in the reactor bed (the range from 1m to 5m of a feed inlet to the highest hot spot temperature of 315 ℃) in the test reaction process, enabling the mixture generated by the reaction to enter a heat exchanger E101 through a discharge hole at the bottom of a fixed bed reactor K101, cooling the reaction mixture subjected to heat exchange by the heat exchanger E101 to 20+/-3 ℃ by a cooler R103, and cooling the cooled liquid to N 2 The mixture enters a high-pressure separator R104 through the control of a regulating valve to carry out gas-liquid phase separation, the liquid part of the high-pressure separator R104 enters a low-pressure separator R106 through the control of the regulating valve, the pressure of the low-pressure separator is regulated to 0.1MPa through the regulating valve, a sampling point A is arranged on the liquid part in the low-pressure separator R106, the liquid part is subjected to qualitative analysis by using a color-mass spectrum, the liquid composition is determined to contain raw materials of cyclopentane, cyclohexane and unreacted cyclopentene through the qualitative analysis, and new color-mass spectrum peaks are generated to be qualitatively classified into cyclopentanone and 2-cyclopentylene cyclopentanone. The conversion of cyclopentene was found to be 87% (based on the number of moles of nitrous oxide charged, if the cyclopentene consumed by the equimolar reaction should theoretically consume 90mol, and 87mol actually consumed), the selectivity to the desired product cyclopentanone was 98.8% based on 87mol/h cyclopentene consumed, and the selectivity to the by-product 2-cyclopentylene cyclopentanone was 0.5%.
The gas part separated by the low-pressure separator R106 is provided with a sampling port B, and the sampling contains N through gas-mass spectrometry qualitative analysis 2 The gas mass percent is more than 99.5%, nitrous oxide is not detected, and the gas part separated by the low-pressure separator R106 contains trace amounts of cyclopentane, cyclohexane and cyclopentene and N by gas chromatography quantitative analysis 2 The gas volume ratio is less than 0.5%. The gas part separated by the high-pressure separator R104 is controlled and regulated to 0.1MPa by a regulating valve F106, enters a cryogenic gas discharge tank R105, is cooled to-5 to-10 ℃, a sampling point C is arranged on the liquid part of the cryogenic gas discharge tank R105, and the condensate contains trace organic liquid which contains cyclopentane, cyclohexane and cyclopentene through analysisThe gas part of the discharge tank R105 is provided with a sampling point D, and the main component of the sampling and color-mass spectrometry qualitative analysis is N 2 The gas contains no nitrous oxide, and contains trace amounts of cyclopentane, cyclohexane and cyclopentene, and the main composition of the quantitative chromatographic detection comprises N 2 The gas contains more than 99.5 percent by mass and less than 0.5 percent of mixture of cyclohexane, cyclopentane and cyclopentene.
The nitrous oxide is completely converted during the reaction.
The low-pressure separator and the gas part of the deep-cooling gas discharge tank R105 are recycled through pressure swing adsorption of organic matters, and are discharged after the nitrogen is detected to be qualified, and the liquid part of the deep-cooling gas discharge tank R105 is recycled.
Examples
The length of the fixed bed reactor is 6m, the inner diameter DN300 of the fixed bed reactor is provided with a cage type heat exchanger of CN209197530U patent, the fixed bed reactor is filled with inert porous aluminum oxide filler with phi 5mm multiplied by 5mm, and the inert porous material has specific surface area of 30-120 m 2 Per gram, pore diameter of 5-20 nm, positive pressure of 170kgf/cm 2 . The fixed bed reactor is externally provided with an asbestos heat preservation layer, the content of nitrous oxide liquid serving as a raw material is more than 99.5%, the content of cyclohexene serving as a raw material is more than or equal to 99.8%, and cyclohexene is prepared into a cyclohexene, cyclopentane and cyclohexane mixture according to the following steps: cyclopentane: cyclohexane=1:1:6 (molar ratio), the molar ratio of cyclohexene to nitrous oxide is 1:0.9, space velocity 100mol/h (in moles of cyclohexene per hour entering the fixed bed reactor). N for devices shown in the process flow diagram 2 3 times of gas displacement, wherein the oxygen content of the gas in the detection device is less than 0.1PPm, and a heat carrier flowing through a cage type heat exchanger of a fixed bed reactor K101 is preheated to 280+/-5 ℃ according to cyclohexene: cyclopentane: the mixture of solvent reactants of cyclohexane=1:1:6 (mol ratio) enters a heat exchanger E101 by a plunger pump, exchanges heat with a product from an outlet of a fixed bed reactor K101, enters a preheater E102 for preheating to 290+/-5 ℃ after exchanging heat, the mixture of solvent reactants reaching 290+/-5 ℃ enters the top of the fixed bed reactor at one time, and nitrous oxide enters the heat exchanger E101 by the plunger pump, exchanges heat with the product from the outlet of the fixed bed reactor K101 and enters the preheater after exchanging heat Preheating the preheater E102 to 290+/-5 ℃, wherein dinitrogen monoxide reaches 290+/-5 ℃ from the top, the middle part and the lower part of the fixed bed reactor, three parts enter the fixed bed reactor K101, the top feeding position refers to the position of 0.0% of the top of the fixed bed reactor K101 from top to bottom, the middle feeding position refers to the position of 30% of the top of the fixed bed reactor K101 from top to bottom, the lower feeding position refers to the position of 60% of the top of the fixed bed reactor K101 from top to bottom, the proportion of the fed dinitrogen monoxide in the three parts accounts for 35%,35%,30% of the total fed dinitrogen monoxide respectively, the temperature of a heat carrier in the fixed bed reactor and the flow rate are regulated to be within the range of 310+/-20 ℃, the pressure in the fixed bed reactor is regulated to be 20MPa by a regulating valve, cyclohexene and dinitrogen monoxide are fully reacted, the temperature of the hot spot temperature is 326% in the reactor bed (the range from 1m to 4m from the feed inlet) in the test reaction process, the mixture 103 is smoothly reacted through the fixed bed reactor K101, the mixture enters the heat exchanger E101 ℃ to be cooled by cooling the heat exchanger E101 to 20 ℃ after the mixture is cooled by cooling the heat exchanger R101 2 The mixture enters a high-pressure separator R104 through the control of a regulating valve to carry out gas-liquid phase separation, the liquid part of the high-pressure separator R104 enters a low-pressure separator R106 through the control of the regulating valve, the pressure of the low-pressure separator is regulated to 0.1MPa through the regulating valve, a sampling point A is arranged on the liquid part of the low-pressure separator R106, the liquid part is subjected to qualitative analysis by using a color-mass spectrum, the liquid composition is determined to contain raw materials of cyclopentane, cyclohexane and unreacted cyclohexene through the qualitative analysis, and new color-mass spectrum peaks are generated to be qualitatively cyclohexanone and 2-cyclohexylidene cyclohexanone. The conversion of cyclohexene monointo 81% (which should be 90mol, in terms of the number of moles of nitrous oxide charged, if the theory of cyclohexene consumed by the equimol reaction should be consumed, 81mol actually consumed) was quantitatively analyzed by chromatography, the selectivity for the desired product cyclohexanone was 98.7% in terms of 81mol/h cyclohexene consumed, and the selectivity for the by-product 2-cyclohexylidene cyclohexanone was 0.4%.
The gas part separated by the low-pressure separator R106 is provided with a sampling port B, and the sampling contains N through gas-mass spectrometry qualitative analysis 2 The mass content of the gas is greater than99.5% of the total amount of nitrous oxide is not detected, and the gas fraction separated by the low-pressure separator R106 is quantitatively analyzed by gas chromatography for trace amounts of cyclopentane, cyclohexane and cyclohexene, and N 2 The gas volume ratio is less than 0.2%. The gas part separated by the high-pressure separator R104 is controlled and regulated to 0.1MPa by a regulating valve F106, enters a deep-cooling gas discharge tank R105, is cooled to-5 to-10 ℃, a sampling point C is arranged on the liquid part of the deep-cooling gas discharge tank R105, a trace amount of organic liquid is contained in condensate, the condensate contains cyclopentane, cyclohexane and cyclohexene through analysis, a sampling point D is arranged on the gas part of the deep-cooling gas discharge tank R105, and the main component of the sample is N through qualitative analysis of color-mass spectrometry 2 The gas contains no nitrous oxide, and contains trace amounts of cyclopentane, cyclohexane and cyclopentene, and the main composition of the quantitative chromatographic detection comprises N 2 The gas has a mass content of more than 99.5% and contains less than 0.1% of a mixture of cyclohexane, cyclopentane and cyclohexene.
The nitrous oxide is completely converted during the reaction.
The low-pressure separator and the gas part of the deep-cooling gas discharge tank R105 are recycled through pressure swing adsorption of organic matters, and are discharged after the nitrogen is detected to be qualified, and the liquid part of the deep-cooling gas discharge tank R105 is recycled.
The summary is as follows:
first, the present invention employs inert porous materials according to the Kelvin equation
Wherein P is Concave recess Represents the saturated vapor pressure of an inert porous material night membrane;
P 0 represents the saturated vapor pressure of the vapor in the liquid planar state;
r Concave recess Represents the radius of the pore size of the inert porous material;
t represents the thermodynamic temperature;
m represents the molecular weight of cycloolefin;
r represents a thermodynamic constant.
Sigma can be regarded as the value of free enthalpy per unit surface at a given temperature, pressure composition, also called surface free enthalpy.
ρ represents the density of the liquid;
n j representing the composition of the liquid.
As can be seen from equation 1, the inert porous material r Concave recess Smaller, at the same T and n j Under the condition of P Concave recess <P 0 A liquid film is formed, in other words, the reaction pressure of the cycloolefin with dinitrogen monoxide is reduced by the presence of the inert porous material.
Secondly, the inert porous material enables cycloolefin to be adsorbed on the surface of the inert porous material to generate a liquid film with large surface area, so that the opportunity of enabling nitrous oxide and cycloolefin to take part in reaction to generate cyclic ketone is provided for the sufficient collision, and the existence of the porous material enables the cycloolefin liquid film to have large surface activation energy, so that the cycloolefin and nitrous oxide react to have sufficient activation energy.
Thirdly, the inert porous material has large specific surface area, can remove branched chain free radicals generated in the reaction process of cycloolefin and nitrous oxide, and avoids explosion reaction.
The three advantages are combined, so that the single-conversion rate of the reaction of the cycloolefin and the nitrous oxide is higher than the conventional level in the prior art.
Conversion definition of bill of materials:
conversion per unit of material defined (%) = (a-B)/a 100%
A: under the stable operation condition of the fixed bed reactor, the temperature, pressure, flow and composition of each bed layer of the fixed bed reactor in unit time have constant values, the mol number of cycloolefin entering from the inlet of the fixed bed reactor in unit time is A, and the mol number of cycloolefin which does not participate in the reaction at the outlet of the fixed bed reactor is B.
The mol number of the cyclic ketone of the target compound is C at the outlet of the fixed bed reactor.
Selectivity definition:
the selectivity (%) of the cyclic ketone of interest compound was =c/(a-B) ×100%.
It should be understood that the foregoing embodiments of the present invention are merely illustrative of the present invention and not limiting, and that various other changes and modifications can be made by one skilled in the art based on the above description, and it is not intended to be exhaustive of all embodiments, and all obvious changes and modifications that come within the spirit of the invention are desired to be protected.
Claims (10)
1. An apparatus for producing cyclic ketones by oxidizing cyclic olefins with nitrous oxide, characterized in that: the device comprises a nitrogen tank (V101), a cycloolefin metering tank (R101), a dinitrogen monoxide metering tank (R102), a heat exchanger (E101), a preheater (E102), a fixed bed reactor (K101), a cooler (R103), a high-pressure separator (R104), a deep cold gas discharge tank (R105) and a low-pressure separator (R106), wherein the cycloolefin metering tank (R101) is provided with a cycloolefin inlet, an outlet of the cycloolefin metering tank (R101) is connected with an inlet of the fixed bed reactor (K101) through a pipeline through the heat exchanger (E101) and the preheater (E102), an outlet of the dinitrogen monoxide metering tank (R102) is provided with a dinitrogen monoxide inlet, an outlet of the fixed bed reactor (K101) is connected with an inlet of the fixed bed reactor (K101) through the heat exchanger (E101) and the preheater (E102), an outlet of the fixed bed reactor (K101) is connected with an inlet of the high-pressure separator (R104) through the pipeline through the heat exchanger (E101) and the cooler (R103), an outlet of the upper end of the high-pressure separator (R104) is connected with an inlet of the cold gas discharge tank (R105) through the pipeline, a lower end of the cold gas discharge tank (R106) is connected with an outlet of the cold gas discharge tank (R106) through the deep cold gas inlet of the cold gas separator (R106), the upper end of the low-pressure separator (R106) is provided with a gas discharge port; the device comprises a cycloolefin metering tank (R101), a nitrous oxide metering tank (R102), a heat exchanger (E101), a preheater (E102), a fixed bed reactor (K101), a cooler (R103), a high-pressure separator (R104), a cryogenic gas discharge tank (R105) and a low-pressure separator (R106), wherein the cycloolefin metering tank, the nitrous oxide metering tank, the heat exchanger (E101), the preheater (E102), the fixed bed reactor (K101), the cooler (R103), the high-pressure separator (R104), the cryogenic gas discharge tank (R105) and the low-pressure separator (R106) are all connected with a nitrogen tank (V101) through pipelines, and the nitrogen tank (V101) is provided with a nitrogen inlet;
The inside of the fixed bed reactor (K101) is provided with a cage type heat exchanger, and the specific structure is as follows: comprises a heat carrier inlet conduit (1), a heat carrier distributing pipe (2), a heat carrier distributing pipe box (3), a heat exchanger tube array, a supporting ring, a heat carrier collecting pipe box (10), a spiral pipe (11), a heat carrier collecting pipe (12) and a heat carrier outlet conduit (13); the heat carrier inlet guide pipe (1) is positioned at the uppermost end of the heat exchanger, the heat carrier inlet guide pipe (1) is connected with a heat carrier distribution pipe (2), the heat carrier distribution pipe (2) is connected with a heat carrier distribution pipe box (3), the heat carrier distribution pipe box (3) is in a ring shape, the heat carrier distribution pipe box (3) is connected with a plurality of groups of concentric heat exchanger tubes which are uniformly distributed circumferentially, the heat exchanger tubes are supported by a plurality of layers of support rings, the lower ends of the heat exchanger tubes are connected with a heat carrier collecting pipe box (10), the lower side of the heat carrier collecting pipe box (10) is connected with a plurality of groups of spiral pipes (11) which are coiled together, the lower end of each spiral pipe (11) is connected with a heat carrier collecting pipe (12), and the other end of each heat carrier collecting pipe (12) is connected to a heat carrier outlet guide pipe (13) at the lowermost end of the heat exchanger; the heat exchanger tube array comprises an inner ring heat exchanger tube array (4), a middle ring heat exchanger tube array (5) and an outer ring heat exchanger tube array (6), and the support ring comprises an inner ring support ring (7), a middle ring support ring (8) and an outer ring support ring (9); the inner ring support ring (7) is provided with ventilation holes (14), the outer ring of the inner ring support ring (7) is provided with inner ring heat exchanger tube array support grooves (15) which are uniformly distributed and have the same number as the inner ring heat exchanger tube arrays (4), and the inner ring heat exchanger tube array support grooves (15) are welded with the inner ring heat exchanger tube arrays (4); the middle ring support ring (8) is provided with a middle ring support ring inner cavity (16), the diameter of the middle ring support ring inner cavity (16) is larger than the outer diameter of the inner ring support ring (7), the outer ring of the middle ring support ring (8) is provided with middle ring heat exchanger tube array support grooves (17) which are uniformly distributed and have the same number as the middle ring heat exchanger tube arrays (5), and the middle ring heat exchanger tube array support grooves (17) are welded with the middle ring heat exchanger tube arrays (5); the outer ring support ring (9) is provided with an outer ring support ring inner cavity (18), the diameter of the outer ring support ring inner cavity (18) is larger than the outer diameter of the middle ring support ring (8), the outer ring of the outer ring support ring (9) is provided with outer ring heat exchanger tube array support grooves (19) which are uniformly distributed and have the same number with the outer ring heat exchanger tubes (6), and the outer ring heat exchanger tube array support grooves (19) are welded with the outer ring heat exchanger tubes (6).
2. The apparatus for producing cyclic ketone by oxidizing cyclic olefin with nitrous oxide according to claim 1, wherein: the bottom ends of the cycloolefin metering tank (R101), the nitrous oxide metering tank (R102), the heat exchanger (E101), the preheater (E102), the fixed bed reactor (K101), the cooler (R103), the high-pressure separator (R104), the cryogenic gas discharge tank (R105) and the low-pressure separator (R106) are provided with low discharge ports.
3. The apparatus for producing cyclic ketone by oxidizing cyclic olefin with nitrous oxide according to claim 1, wherein: the outlet pipeline of the cycloolefin metering tank (R101) is provided with a cycloolefin metering booster pump (P101), the outlet pipeline of the nitrous oxide metering tank (R102) is provided with a nitrous oxide metering booster pump (P102), the outlet pipeline of the fixed bed reactor (K101) is provided with a filter (F101), and the inlet pipeline of the fixed bed reactor (K101) is also connected with a nitrogen tank (V101).
4. A process for producing cyclic ketones using the apparatus of claim 1 by oxidizing cyclic olefins with dinitrogen monoxide, characterized in that: adding an inert porous material into a fixed bed reactor (K101), continuously introducing cycloolefin or a mixture of cycloolefin and saturated alkane and nitrous oxide into the fixed bed reactor (K101) through a heat exchanger (E101) and a preheater (E102) at the reaction temperature of 100-350 ℃ and the reaction pressure of 5-30 MPa, wherein the mol ratio of cycloolefin to nitrous oxide is 1:0.05-1:0.9, and carrying out the following reaction:
C n H 2n-2 (cycloolefin) +N 2 O (nitrous oxide) C n H 2n-2 O (product cyclic ketone) +N 2 ∈ (Nitrogen)
Wherein: n is a positive integer of 4 to 20;
reaction product cyclic ketone and unreacted starting material and N produced 2 Heat exchange with the reaction raw material through a heat exchanger (E101), cooling the reaction product to 0-35 ℃ through a cooler (R103), separating gas from liquid through a high-pressure separator (R104), separating residual gas again after the liquid phase part enters a low-pressure separator (R106), and separating the gas part separated by the low-pressure separator (R106) into N 2 The liquid fraction of the product separated by the low-pressure separator (R106) containing cyclic ketones C n H 2n-2 Separating out liquid part product containing cyclic ketone from low pressure separator (R106) for rectification, detecting cyclic ketone product by color-mass spectrum and chromatographic analysis, recycling light cyclic olefin and saturated alkane obtained by rectification, condensing gas phase component in high pressure separator (R104) in cryogenic gas discharge tank (R105) at-10-10deg.C, separating and recycling by condensing liquid part rectification device, and separating and recycling by-product N separated by cryogenic gas discharge tank 2 And (5) discharging.
5. The method for producing cyclic ketone by oxidizing cyclic olefin with nitrous oxide according to claim 4, wherein: after the inert porous material is added into the fixed bed reactor (K101), N in a nitrogen tank (V101) is needed before the reaction starts 2 Purging the entire apparatus, at N 2 The subsequent reaction is carried out under protection, after the mixture of cycloolefin or cycloolefin and saturated alkane and nitrous oxide pass through a heat exchanger (E101), the temperature reaches 100-200 ℃, after the mixture passes through a preheater (E102), the temperature reaches 210-350 ℃, the reaction temperature in a fixed bed reactor (K101) is controlled, the reaction is carried out under the condition of 100-350 ℃, the pressure in the fixed bed reactor (K101) is 5-30 MPa, and the materials entering a cooler (R103) are cooledThe cooler (R103) is cooled to 0-35 ℃.
6. The method for producing cyclic ketone by oxidizing cyclic olefin with nitrous oxide according to claim 4, wherein: the heat carrier at 100-350 ℃ is introduced into the cage type heat exchanger and is used for removing heat released in the reaction process of cycloolefin and nitrous oxide, an inert porous material is added into the inner cavity of the fixed bed reactor, the fixed bed reactor is a tubular fixed bed reactor, a jacket layer is arranged outside the tubular fixed reactor, the heat carrier at 100-350 ℃ is arranged in the jacket, and the heat released in the reaction process of cycloolefin and nitrous oxide is removed by the heat carrier; the tube type fixed bed reactor is a single tube or multi-tube parallel fixed bed reactor.
7. The method for producing cyclic ketone by oxidizing cyclic olefin with nitrous oxide according to claim 4, wherein: the inert porous material is one or more of porous ceramic, porous glass or porous aluminum oxide, the structure of the inert porous material is cylindrical or spherical, the size of the cylindrical is phi 5mm multiplied by 5 mm-phi 20mm multiplied by 20mm, the radius R of the spherical is 5 mm-20 mm, and the inert porous material has a specific surface area of 30-260 m 2 Per g, pore diameter 5-300 nm, positive pressure intensity>150kgf/cm 2 。
8. The method for producing cyclic ketone by oxidizing cyclic olefin with nitrous oxide according to claim 7, wherein: the inert porous material has a specific surface area of 30-170 m 2 And/g, pore diameter is 5-230 nm.
9. The method for producing cyclic ketone by oxidizing cyclic olefin with nitrous oxide according to claim 4, wherein: the cycloolefin is C 4 ～C 2O Monocyclomonoolefins of the formula C n H 2n-2 Wherein n=a positive integer from 4 to 20; cycloolefins are pure cycloolefins or mixtures of cycloolefins containing saturated alkanes, when cycloolefins are mixtures of cycloolefins containing saturated alkanes, the molar ratio of cycloolefins to saturated alkanesIs 1: 1-1: 30, the saturated alkane is C 4 ～C 2O Mono-, linear-or branched-chain alkanes.
10. The method for producing cyclic ketone by oxidizing cyclic olefin with nitrous oxide according to claim 4, wherein: the fixed bed reactor (K101) is a vertical reactor, the mixture of cycloolefin or cycloolefin and saturated alkane is injected from the top of the fixed bed reactor (K101) at one time, nitrous oxide is injected from the top of the fixed bed reactor (K101) at one time, or nitrous oxide is injected into the fixed bed reactor (K101) from 3 positions of the top, the middle and the lower part of the fixed bed reactor (K101), the top feeding position refers to the position of 0.0% -20% of the top of the fixed bed reactor (K101) from top to bottom, the middle feeding position refers to the position of 20% -40% of the top of the fixed bed reactor (K101) from top to bottom, the lower feeding position refers to the position of 40% -70% of the top of the fixed bed reactor (K101) from top to bottom, and the proportion of the fed amount of nitrous oxide at three positions accounts for 20% -40% of the total fed amount of nitrous oxide respectively, or the position of 0.0% -70% of the fed nitrous oxide is evenly injected from the top of the fixed bed reactor (K101).
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