CN112174778A - System and process for enhancing catalytic-free oxidation of cyclooctane - Google Patents
System and process for enhancing catalytic-free oxidation of cyclooctane Download PDFInfo
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- CN112174778A CN112174778A CN201910600997.7A CN201910600997A CN112174778A CN 112174778 A CN112174778 A CN 112174778A CN 201910600997 A CN201910600997 A CN 201910600997A CN 112174778 A CN112174778 A CN 112174778A
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- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000004914 cyclooctane Substances 0.000 title claims abstract description 153
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 67
- 230000003647 oxidation Effects 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000002708 enhancing effect Effects 0.000 title claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 79
- 239000001301 oxygen Substances 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 239000007788 liquid Substances 0.000 claims abstract description 53
- 239000000839 emulsion Substances 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000012545 processing Methods 0.000 claims abstract description 8
- 238000012546 transfer Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 7
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 claims description 29
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 28
- 238000003860 storage Methods 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 19
- 238000007599 discharging Methods 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 11
- 230000001965 increasing effect Effects 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012263 liquid product Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 238000005728 strengthening Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000005501 phase interface Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000004581 coalescence Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
- B01F23/235—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids for making foam
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
- B01F23/2366—Parts; Accessories
- B01F23/2368—Mixing receptacles, e.g. tanks, vessels or reactors, being completely closed, e.g. hermetically closed
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
- B01F23/237—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media
- B01F23/2373—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media for obtaining fine bubbles, i.e. bubbles with a size below 100 µm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/30—Micromixers
- B01F33/304—Micromixers the mixing being performed in a mixing chamber where the products are brought into contact
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
- B01J10/002—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor carried out in foam, aerosol or bubbles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—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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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
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- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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Abstract
The invention provides a system and a process for strengthening the oxidation of cyclooctane without a catalyst, which comprises the following steps: a micro-interface generator, a reaction vessel, a feeding unit and a product processing unit. Compared with the prior art, the catalyst-free oxidation strengthening system for cyclooctane has the beneficial effects that the micro-interface generator is added into the catalyst-free oxidation strengthening system for cyclooctane, oxygen is crushed into gas with the diameter of 1 mu m or more and d <1mm, a micro-bubble system is formed, and micro-bubbles have additional pressure, so that coalescence is difficult to occur, and gas-liquid emulsion is obtained in the gas-liquid mixing process, so that a higher phase interface area is formed in a reaction container, the mass transfer efficiency is improved, the oxygen and cyclooctane are fully reacted, and the yield of products is improved.
Description
Technical Field
The invention relates to the technical field of non-catalyst oxidation of cyclooctane, in particular to a system and a process for strengthening the non-catalyst oxidation of the cyclooctane.
Background
At present, the preparation of cyclooctanol and cyclooctanone by catalytic oxidation of cyclooctane is an important chemical conversion process in chemical industry, and the market demand is large. Wherein O is2Because of the advantages of low price, easy obtaining, high atom economy and the like, the catalyst is the best choice for the catalytic oxidation of the cyclooctane, but O is used at present2Cyclooctane oxidation systems which are oxidizers are often carried out using catalysts to promote the reaction, e.g. metal complex catalysis, metal nanoparticle catalysis, metal oxide particle catalysis, molecular sieve catalysis, carbon material catalysis, photo-promoted catalysisHeteropolyacid catalysis, metal-organic framework material catalysis, and the like. The use of catalytic systems undoubtedly increases the cost of oxidation of cyclooctane and causes additional environmental pollution problems, which are not favorable for the large-scale development of products downstream of the oxidation product of cyclooctane. However, the catalyst-free oxidation often results in low yields of cyclooctanol and cyclooctanone, which cannot meet the requirements, and can cause the waste of cyclooctane.
Disclosure of Invention
In view of this, the invention provides a system and a process for enhancing the oxidation of cyclooctane without a catalyst, and aims to solve the problem of low product yield of the existing oxidation reaction of cyclooctane without a catalyst.
In one aspect, the present invention provides a system for enhancing the catalyst-free oxidation of cyclooctane, comprising: the reactor comprises a micro-interface generator, a reaction vessel, a feeding unit and a product processing unit; wherein the content of the first and second substances,
the micro-interface generator is connected with the feeding unit and is used for converting the pressure energy of oxygen and/or the kinetic energy of cyclooctane into the surface energy of oxygen bubbles, so that the oxygen bubbles are crushed into micro-bubbles with the diameter of 1 mu m or more and d less than 1mm, and the micro-bubbles and the cyclooctane are mixed to form a gas-liquid emulsion, thereby increasing the mass transfer area between the oxygen and the cyclooctane and leading the cyclooctane to fully react with the oxygen under the condition of no catalyst;
the reaction container is connected with the micro-interface generator and is used as a reaction site for the catalyst-free oxidation of the cyclooctane;
the feeding unit is used for conveying cyclooctane and oxygen into the micro-interface generator;
and the product treatment unit is connected with the reaction container and is used for treating the mixture obtained by the catalyst-free oxidation reaction of the cyclooctane.
Further, in the system for enhancing the oxidation of cyclooctane without the catalyst, the micro-interface generator is selected from one or more of a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator.
Further, in the above system for enhancing the catalytic-free oxidation of cyclooctane, the feed unit comprises: a liquid phase feed unit and a gas phase feed unit;
the liquid-phase feeding unit is connected with the micro-interface generator and is used for conveying cyclooctane into the micro-interface generator;
the gas-phase feeding unit is connected with the micro-interface generator and is used for conveying oxygen into the micro-interface generator.
Further, in the above-mentioned system for intensifying the catalyst-free oxidation of cyclooctane, the liquid-phase feeding unit comprises: a cyclooctane storage tank and a first pump; wherein the content of the first and second substances,
the cyclooctane storage tank is used for storing cyclooctane;
the first pump is respectively connected with the cyclooctane storage tank and the micro-interface generator and is used for conveying the cyclooctane from the cyclooctane storage tank to the micro-interface generator.
Further, in the above system for enhancing the oxidation of cyclooctane without a catalyst, the product treatment unit comprises: a second pump, a filter tank and a rectifying tower; wherein the content of the first and second substances,
the second pump is connected with the reaction container and is used for conveying the mixture obtained by the catalyst-free oxidation reaction of the cyclooctane from the reaction container to the filter tank;
the filter tank is connected with the second pump and is used for separating solid products and liquid products contained in the products;
the rectifying tower is connected with the filtering tank and is used for decompressing, rectifying and separating the cyclooctanone and the cyclooctanol.
Further, in the above-mentioned system for enhancing the oxidation of cyclooctane without catalyst, the rectifying tower is provided with two discharge ports for discharging cyclooctanone and cyclooctanol outside the tower respectively.
Compared with the prior art, the catalyst-free oxidation strengthening system for cyclooctane has the beneficial effects that the micro-interface generator is added into the catalyst-free oxidation strengthening system for cyclooctane, oxygen is crushed into gas with the diameter of 1 mu m or more and d <1mm, a micro-bubble system is formed, and micro-bubbles have additional pressure, so that coalescence is difficult to occur, and gas-liquid emulsion is obtained in the gas-liquid mixing process, so that a higher phase interface area is formed in a reaction container, the mass transfer efficiency is improved, the oxygen and cyclooctane are fully reacted, and the yield of products is improved.
Furthermore, the micro-interface generator is applied to the intensified system for the oxidation of the cyclooctane without the catalyst, so that the cost of the catalyst is saved, the reaction is easy to control, and the harm of the catalyst to air is reduced.
Furthermore, the liquid-phase feeding unit is provided with a feeding pump, and when the system runs, the feeding pump can respectively provide power for the transportation of the cyclooctane, so that the cyclooctane can be conveyed to a designated device at a designated speed, and the running efficiency of the system is improved.
The process for the catalyst-free oxidation of cyclooctane is characterized by comprising the following steps of:
preparation of reactants: pumping a certain amount of cyclooctane from a cyclooctane storage tank into a micro-interface generator through a first pump, and simultaneously conveying a certain amount of oxygen with preset pressure from an oxygen storage tank into the micro-interface generator; the micro-interface generator converts the pressure energy of oxygen and/or the kinetic energy of cyclooctane into the surface energy of oxygen bubbles, so that the oxygen bubbles are broken into micro-bubbles, and the micro-bubbles and the cyclooctane are mixed to form gas-liquid emulsion, thereby increasing the interfacial area of the oxygen and the cyclooctane;
preparation of cyclooctanone and cyclooctanol: conveying the gas-liquid emulsion into a reaction container, slowly raising the temperature in the reaction container to a preset initial temperature, fully reacting the gas-liquid emulsion, cooling the temperature in the reaction container to room temperature after the reaction is finished, introducing a mixture obtained by the catalyst-free oxidation reaction of cyclooctane into a filter tank, performing solid-liquid separation on the mixture by the filter tank, discharging the separated solid from the bottom of the filter tank, introducing the separated liquid into a rectifying tower for reduced pressure rectification, taking a fraction of 70-80 ℃ below 20mmHg, namely cyclooctanone, and taking a fraction of 120-130 ℃ below 22mmHg, namely cyclooctanol.
Further, in the process of the catalyst-free oxidation of cyclooctane, the preset pressure of oxygen is in the range of 0.2MPa to 1.0 MPa.
Further, in the process for the catalyst-free oxidation of cyclooctane, the preset initial temperature is 120-150 ℃.
According to the process for the catalyst-free oxidation of the cyclooctane, the micro-interface generator is added into the strengthening system for the catalyst-free oxidation of the cyclooctane, oxygen is crushed into gas with the diameter of 1 mu m or less and d of 1mm to form a micro-bubble system, and the micro-bubbles have additional pressure, so that the micro-bubbles are difficult to coalesce, and gas-liquid emulsion is obtained in the gas-liquid mixing process, so that a higher phase interface area is formed in a reaction container, the mass transfer efficiency is improved, the oxygen and the cyclooctane are fully reacted, and the yield of the product is improved.
Furthermore, the process saves the cost of the catalyst by using the micro-interface generator, simultaneously enables the reaction to be easy to control, and simultaneously reduces the harm of the catalyst to air.
Furthermore, the process for the oxidation of cyclooctane without the catalyst provided by the invention has the advantages that the mixture after the reaction in the reaction vessel is firstly introduced into the filtering tank for filtering, then introduced into the rectifying tower for vacuum rectification, and the fraction of 70-80 ℃ under 20mmHg is taken as cyclooctanone, the fraction of 120-130 ℃ under 22mmHg is taken as cyclooctanol, so that the operation is simple, and the products can be sequentially separated.
Furthermore, the process for the catalyst-free oxidation of cyclooctane provided by the invention limits the temperature and the pressure of oxygen in the reaction container, ensures that gas-liquid emulsion in the reaction container can react efficiently, controls the energy consumption of the system to be the lowest, and can further reduce the energy consumption of the system.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
fig. 1 is a schematic structural diagram of an enhancement system for catalytic-free oxidation of cyclooctane according to an embodiment of the present invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Referring to fig. 1, an enhancing system for catalytic-free oxidation of cyclooctane according to an embodiment of the present invention comprises: a micro-interface generator 4, a reaction vessel 5, a feeding unit and a product processing unit; the micro-interface generator 4 is connected with the feeding unit and is used for converting the pressure energy of oxygen and/or the kinetic energy of cyclooctane into the surface energy of oxygen bubbles, breaking the oxygen bubbles into microbubbles, and mixing the microbubbles and the cyclooctane to form a gas-liquid emulsion, so that the mass transfer area between oxygen and cyclooctane is increased, and the cyclooctane fully reacts with the oxygen under the condition of no catalyst; the reaction container 5 is connected with the micro-interface generator 4 and is used as a reaction site for the catalyst-free oxidation of cyclooctane; the feeding unit is used for conveying cyclooctane and oxygen into the micro-interface generator 4; the product treatment unit is connected with the reaction vessel 5 and is used for treating the mixture obtained by the catalyst-free oxidation reaction of the cyclooctane.
When the system moves, the feed unit starts to carry its inside reactant of storing extremely little interface generator 4, little interface generator 4 can smash oxygen, makes oxygen breakage to the micron yardstick, forms the diameter and is 1 mu m ≤ d ≤ 1 mm's microbubble, and after the breakage is accomplished, little interface generator 4 mixes microbubble and cyclooctane and forms the gas-liquid emulsion, and little interface generator 4 exports the gas-liquid emulsion to reaction vessel 5 after the gas-liquid emulsion mixes the completion, through control temperature in the reaction vessel 5, the pressure of oxygen carry out high efficiency reaction in reaction vessel 5, and reaction vessel 5 exports the mixture that generates to product processing unit, and product processing unit is right the mixture carries out subsequent processing.
It should be understood that, in this embodiment, the number and the type of the micro-interface generators 4 are not specifically limited, and may be selected from one or more of a pneumatic micro-interface generator, a hydraulic micro-interface generator, and a gas-liquid linkage micro-interface generator, and the type of the reaction vessel 5 is not limited, so long as it can provide a place for the enhanced reaction of the catalytic-free oxidation of the cyclooctane.
With continued reference to fig. 1, the feed unit includes: a liquid-phase feeding unit, a gas-phase feeding unit 3; the liquid phase feeding unit is connected with the micro-interface generator 4 and is used for conveying cyclooctane into the micro-interface generator 4; the gas phase feed unit 3 is connected to the micro-interface generator 4 for delivering oxygen into the micro-interface generator 4.
Specifically, the liquid-phase feed unit includes: a cyclooctane storage tank 1 and a first pump 2; wherein, the cyclooctane storage tank 1 is a tank body for storing the cyclooctane; the first pump 2 is respectively connected with the cyclooctane storage tank 1 and the micro-interface generator 4 and is used for conveying the cyclooctane from the cyclooctane storage tank 1 to the micro-interface generator 4; it is understood that the cyclooctane storage tank 1 may be a metal tank or a non-metal tank as long as the cyclooctane storage tank 1 can be loaded with a specified amount of cyclooctane. Meanwhile, the type and power of the first pump 2 are not particularly limited as long as the first pump 2 can deliver cyclooctane at a specified flow rate.
With continued reference to FIG. 1, the product processing unit includes: a second pump 6, a filter tank 7 and a rectifying tower 8; wherein the second pump 6 is connected with the reaction vessel 5 and is used for conveying the mixture obtained by the catalyst-free oxidation reaction of the cyclooctane from the reaction vessel 5 to the filter tank 7; the filter tank 7 is connected with the second pump 6 and is used for separating solid products and liquid products contained in the mixture obtained by the catalytic-free oxidation reaction of the cyclooctane, wherein the solid products are discharged from the bottom of the filter tank 7, and the liquid products are conveyed to the rectifying tower 8; the rectifying tower 8 is connected with the filtering tank 7 and is provided with a discharge port 9 and a discharge port 10 which are respectively used for discharging the cyclooctanone and the cyclooctanol outside the tower and are used for decompressing, rectifying and separating the cyclooctanone and the cyclooctanol. It is understood that the filter tank 7 may be a metal tank or a non-metal tank, as long as it is sufficient to separate the mixture obtained by the reaction, and the type and power of the second pump 6 are not particularly limited, as long as it is sufficient that the second pump 6 can deliver oxygen at a specified flow rate.
Compared with the prior art, the catalyst-free oxidation strengthening system for cyclooctane has the beneficial effects that the micro-interface generator 4 is added into the catalyst-free oxidation strengthening system for cyclooctane, oxygen is crushed into gas with the diameter d being more than or equal to 1 mu m and less than 1mm to form a micro-bubble system, and micro-bubbles have additional pressure, so that coalescence is difficult to occur, and gas-liquid emulsion is obtained in the gas-liquid mixing process, so that a higher phase interface area is formed in the reaction container 5, the mass transfer efficiency is improved, the oxygen and cyclooctane are fully reacted, and the yield of the product is improved.
Furthermore, the micro-interface generator 4 is applied to the intensified system for the oxidation of the cyclooctane without the catalyst, so that the cost of the catalyst is saved, the reaction is easy to control, and the harm of the catalyst to the air is reduced.
Furthermore, the liquid-phase feeding unit is provided with a feeding pump, and when the system runs, the feeding pump can respectively provide power for the transportation of the cyclooctane, so that the cyclooctane can be conveyed to a designated device at a designated speed, and the running efficiency of the system is improved.
The method and effect of the present invention for enhancing the catalytic oxidation of cyclooctane will be further illustrated with reference to the following specific examples.
A process for the catalyst-free oxidation of cyclooctane comprises the following steps:
preparation of reactants: pumping a certain amount of cyclooctane from a cyclooctane storage tank 1 into a micro-interface generator 4 through a first pump 2, and simultaneously conveying a certain amount of oxygen with the pressure of 0.2 MPa-1.0MPa from an oxygen storage tank into the micro-interface generator 4; the micro-interface generator 4 converts the pressure energy of the oxygen and/or the kinetic energy of the cyclooctane into the surface energy of the oxygen bubbles, so that the oxygen bubbles are broken into micro-bubbles, and the micro-bubbles and the cyclooctane are mixed to form gas-liquid emulsion, thereby increasing the interfacial area of the oxygen and the cyclooctane;
preparation of cyclooctanone and cyclooctanol: conveying the gas-liquid emulsion into a reaction container 5, slowly raising the temperature in the reaction container 5 to 120-150 ℃, fully reacting the gas-liquid emulsion, cooling the temperature in the reaction container 5 to room temperature after the reaction is finished, introducing a mixture obtained by the catalyst-free oxidation reaction of cyclooctane into a filter tank 7, carrying out solid-liquid separation on the mixture by the filter tank 7, discharging the separated solid from the bottom of the filter tank 7, introducing the separated liquid into a rectifying tower 8 for reduced pressure rectification, taking a fraction of 70-80 ℃ below 20mmHg, namely cyclooctanone, and taking a fraction of 120-130 ℃ below 22mmHg, namely cyclooctanol.
Example 1
Pumping a certain amount of cyclooctane from a cyclooctane storage tank 1 into a micro interface generator 4 through a first pump 2, and simultaneously conveying a certain amount of oxygen with the pressure of 0.2MPa from an oxygen storage tank into the micro interface generator 4; the micro-interface generator 4 converts the pressure energy of the oxygen and/or the kinetic energy of the cyclooctane into the surface energy of the oxygen bubbles, so that the oxygen bubbles are broken into micro-bubbles, and the micro-bubbles and the cyclooctane are mixed to form gas-liquid emulsion, thereby increasing the interfacial area of the oxygen and the cyclooctane;
preparation of cyclooctanone and cyclooctanol: conveying the gas-liquid emulsion into a reaction container 5, slowly raising the temperature in the reaction container 5 to 120 ℃, fully reacting the gas-liquid emulsion, cooling the temperature in the reaction container 5 to room temperature after the reaction is finished, introducing a mixture obtained by the catalyst-free oxidation reaction of cyclooctane into a filter tank 7, performing solid-liquid separation on the mixture by the filter tank 7, discharging the separated solid from the bottom of the filter tank 7, introducing the separated liquid into a rectifying tower 8 for reduced pressure rectification, and taking a fraction of 70-80 ℃ below 20mmHg, namely the cyclooctanone, wherein the yield of the cyclooctanone is 12.1%; taking the fraction of 120-130 ℃ under 22mmHg, namely the cyclooctanol, wherein the yield of the cyclooctanol is 2.6 percent.
Example 2
Pumping a certain amount of cyclooctane from a cyclooctane storage tank 1 into a micro interface generator 4 through a first pump 2, and simultaneously conveying a certain amount of oxygen with the pressure of 0.6MPa from an oxygen storage tank into the micro interface generator 4; the micro-interface generator 4 converts the pressure energy of the oxygen and/or the kinetic energy of the cyclooctane into the surface energy of the oxygen bubbles, so that the oxygen bubbles are broken into micro-bubbles, and the micro-bubbles and the cyclooctane are mixed to form gas-liquid emulsion, thereby increasing the interfacial area of the oxygen and the cyclooctane;
preparation of cyclooctanone and cyclooctanol: conveying the gas-liquid emulsion into a reaction container 5, slowly raising the temperature in the reaction container 5 to 120 ℃, fully reacting the gas-liquid emulsion, cooling the temperature in the reaction container 5 to room temperature after the reaction is finished, introducing a mixture obtained by the catalyst-free oxidation reaction of cyclooctane into a filter tank 7, performing solid-liquid separation on the mixture by the filter tank 7, discharging the separated solid from the bottom of the filter tank 7, introducing the separated liquid into a rectifying tower 8 for reduced pressure rectification, and taking a fraction of 70-80 ℃ below 20mmHg, namely the cyclooctanone, wherein the yield of the cyclooctanone is 14.2%; taking the fraction of 120-130 ℃ under 22mmHg, namely the cyclooctanol, wherein the yield of the cyclooctanol is 3.5 percent.
Example 3
Pumping a certain amount of cyclooctane from a cyclooctane storage tank 1 into a micro interface generator 4 through a first pump 2, and simultaneously conveying a certain amount of oxygen with the pressure of 1.0MPa from an oxygen storage tank into the micro interface generator 4; the micro-interface generator 4 converts the pressure energy of the oxygen and/or the kinetic energy of the cyclooctane into the surface energy of the oxygen bubbles, so that the oxygen bubbles are broken into micro-bubbles, and the micro-bubbles and the cyclooctane are mixed to form gas-liquid emulsion, thereby increasing the interfacial area of the oxygen and the cyclooctane;
preparation of cyclooctanone and cyclooctanol: conveying the gas-liquid emulsion into a reaction container 5, slowly raising the temperature in the reaction container 5 to 150 ℃, fully reacting the gas-liquid emulsion, cooling the temperature in the reaction container 5 to room temperature after the reaction is finished, introducing a mixture obtained by the catalyst-free oxidation reaction of cyclooctane into a filter tank 7, performing solid-liquid separation on the mixture by the filter tank 7, discharging the separated solid from the bottom of the filter tank 7, introducing the separated liquid into a rectifying tower 8 for reduced pressure rectification, and taking a fraction of 70-80 ℃ below 20mmHg, namely the cyclooctanone, wherein the yield of the cyclooctanone is 16.4%; taking the fraction of 120-130 ℃ under 22mmHg, namely the cyclooctanol, wherein the yield of the cyclooctanol is 5.0 percent.
Comparative example 1
Conveying the cyclooctane and oxygen into a reaction container, slowly raising the temperature in the reaction container to 140 ℃, reacting the cyclooctane and the oxygen with the pressure of 1.2MPa in the reaction container, cooling the temperature in the reaction container to room temperature after the reaction is finished, introducing a mixture obtained by the catalyst-free oxidation reaction of the cyclooctane into a filter tank, carrying out solid-liquid separation on the mixture by the filter tank, discharging the separated solid from the bottom of the filter tank, introducing the separated liquid into a rectifying tower for reduced pressure rectification, taking a fraction of 70-80 ℃ below 20mmHg, namely the cyclooctanone, wherein the yield of the cyclooctanone is 16.4%; taking the fraction of 120-130 ℃ under 22mmHg, namely the cyclooctanol, wherein the yield of the cyclooctanol is 5.0 percent.
Comparative example 2
Conveying the cyclooctane and oxygen into a reaction container, slowly raising the temperature in the reaction container to 110 ℃, reacting the cyclooctane and the oxygen with the pressure of 1.2MPa in the reaction container under the catalytic action of cobalt porphyrin, cooling the temperature in the reaction container to room temperature after the reaction is finished, introducing a mixture obtained by the catalyst-free oxidation reaction of the cyclooctane into a filter tank, carrying out solid-liquid separation on the mixture by the filter tank, discharging the separated solid from the bottom of the filter tank, introducing the separated liquid into a rectifying tower for reduced pressure rectification, taking a fraction of 70-80 ℃ below 20mmHg, namely the cyclooctanone, wherein the yield of the cyclooctanone is 10.1%; taking the fraction of 120-130 ℃ under 22mmHg, namely the cyclooctanol, wherein the yield of the cyclooctanol is 2.3 percent.
Obviously, as can be seen from the comparison between the above examples and comparative examples, in the examples, the micro-interface generator is used to crush the oxygen into micro-bubbles with a diameter d of 1 μm or more and d of less than 1mm, and the micro-bubbles are mixed with the cyclooctane to form a gas-liquid emulsion, so that the mass transfer area between the oxygen and the cyclooctane is increased, and the cyclooctane is fully reacted with the oxygen in the absence of the catalyst; the yields of cyclooctanone and cyclooctanol were significantly higher than in the comparative example.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. An enhancement system for the catalyst-free oxidation of cyclooctane, comprising: the reactor comprises a micro-interface generator, a reaction vessel, a feeding unit and a product processing unit; wherein the content of the first and second substances,
the micro-interface generator is connected with the feeding unit and is used for converting the pressure energy of oxygen and/or the kinetic energy of cyclooctane into the surface energy of oxygen bubbles, so that the oxygen bubbles are crushed into micro-bubbles with the diameter of 1 mu m or more and d less than 1mm, and the micro-bubbles and the cyclooctane are mixed to form a gas-liquid emulsion, thereby increasing the mass transfer area between the oxygen and the cyclooctane and leading the cyclooctane to fully react with the oxygen under the condition of no catalyst;
the reaction container is connected with the micro-interface generator and is used as a reaction site for the catalyst-free oxidation of the cyclooctane;
the feeding unit is used for conveying cyclooctane and oxygen into the micro-interface generator;
and the product treatment unit is connected with the reaction container and is used for treating the mixture obtained by the catalyst-free oxidation reaction of the cyclooctane.
2. The system for enhancing the catalyst-free oxidation of cyclooctane according to claim 1, wherein the micro-interface generator is selected from one or more of a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator.
3. The system for enhancing the catalyst-free oxidation of cyclooctane as claimed in claim 1, wherein the feed unit comprises: a liquid phase feed unit and a gas phase feed unit; wherein the content of the first and second substances,
the liquid-phase feeding unit is connected with the micro-interface generator and is used for conveying cyclooctane into the micro-interface generator;
the gas-phase feeding unit is connected with the micro-interface generator and is used for conveying oxygen into the micro-interface generator.
4. The system for enhancing the catalyst-free oxidation of cyclooctane according to claim 3, wherein the liquid phase feed unit comprises: a cyclooctane storage tank and a first pump; wherein the content of the first and second substances,
the cyclooctane storage tank is used for storing cyclooctane;
the first pump is respectively connected with the cyclooctane storage tank and the micro-interface generator and is used for conveying the cyclooctane from the cyclooctane storage tank to the micro-interface generator.
5. The system for enhancing the catalyst-free oxidation of cyclooctane as claimed in claim 1, wherein the product treatment unit comprises: a second pump, a filter tank and a rectifying tower; wherein the content of the first and second substances,
the second pump is connected with the reaction container and is used for conveying the mixture obtained by the catalyst-free oxidation reaction of the cyclooctane from the reaction container to the filter tank;
the filter tank is connected with the second pump and is used for separating solid products and liquid products contained in the mixture obtained by the catalyst-free oxidation reaction of the cyclooctane;
the rectifying tower is connected with the filtering tank and is used for decompressing, rectifying and separating the cyclooctanone and the cyclooctanol.
6. The system for enhancing the catalyst-free oxidation of cyclooctane according to claim 5, wherein the rectifying tower is provided with two discharge ports for discharging cyclooctanone and cyclooctanol out of the tower, respectively.
7. The process for the catalyst-free oxidation of cyclooctane is characterized by comprising the following steps:
preparation of reactants: pumping a certain amount of cyclooctane from a cyclooctane storage tank into a micro-interface generator through a first pump, and simultaneously conveying a certain amount of oxygen with preset pressure from an oxygen storage tank into the micro-interface generator; the micro-interface generator converts the pressure energy of oxygen and/or the kinetic energy of cyclooctane into the surface energy of oxygen bubbles, so that the oxygen bubbles are broken into micro-bubbles, and the micro-bubbles and the cyclooctane are mixed to form gas-liquid emulsion, thereby increasing the interfacial area of the oxygen and the cyclooctane;
preparation of cyclooctanone and cyclooctanol: conveying the gas-liquid emulsion into a reaction container, slowly raising the temperature in the reaction container to a preset initial temperature, fully reacting the gas-liquid emulsion, cooling the temperature in the reaction container to room temperature after the reaction is finished, introducing a mixture obtained by the catalyst-free oxidation reaction of cyclooctane into a filter tank, performing solid-liquid separation on the mixture by the filter tank, discharging the separated solid from the bottom of the filter tank, introducing the separated liquid into a rectifying tower for reduced pressure rectification, taking a fraction of 70-80 ℃ below 20mmHg, namely cyclooctanone, and taking a fraction of 120-130 ℃ below 22mmHg, namely cyclooctanol.
8. The process for the catalyst-free oxidation of cyclooctane as claimed in claim 7, wherein the predetermined pressure of oxygen is in the range of 0.2MPa to 1.0 MPa.
9. The process for the catalyst-free oxidation of cyclooctane according to claim 7, wherein the predetermined initial temperature is 120 ℃ to 150 ℃.
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