CN110128260A - A kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid - Google Patents
A kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid Download PDFInfo
- Publication number
- CN110128260A CN110128260A CN201910530479.2A CN201910530479A CN110128260A CN 110128260 A CN110128260 A CN 110128260A CN 201910530479 A CN201910530479 A CN 201910530479A CN 110128260 A CN110128260 A CN 110128260A
- Authority
- CN
- China
- Prior art keywords
- air
- tower
- reaction
- oxidation
- adipic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid, this method is that the raw materials such as hexamethylene are added in reaction tower and heat reaction tower, air is passed through from the air intake of air chest simultaneously, air is pumped into reaction tower by force (forcing) pump and carries out oxidation reaction with hexamethylene, after oxidation reaction residual air passes sequentially through gas-liquid separation tower liquid separation, condensing tower condensing recovery organic principle and pressure reducing valve decompression, recycled into air chest；When reaction tower pressure interior force is stablized, stopping is passed through air from air intake, while being passed through oxygen from oxygen intake and continuing oxidation reaction, until hexamethylene conversion is complete.This method realizes that Organic Ingredients is recycled by designing reasonable nitrogen cycle device, not only environmentally friendly, and reduces significant loss, while realizing low energy consumption, reduces cost, also improves the control ability of reaction, be conducive to industrialized production.
Description
Technical field
The present invention relates to a kind of methods of air oxidation of cyclohexane synthesizing adipic acid, in particular to utilize nitrogen circulation process
It improves raw material availability and the method for reducing energy consumption during air oxidation of cyclohexane synthesizing adipic acid, belongs to petrochemical industry skill
Art field.
Background technique
Adipic acid is the basic chemical raw materials of Buddhist nun's human relations 66.Industrially, cyclohexanone liquid phase nitric acid oxidation prepares adipic acid
Main method.The technique that nitric acid oxidation cyclohexanone prepares adipic acid makees raw material using high-cost cyclohexanone, and nitric acid can be rotten
Simultaneously there is environmental pollution in erosion equipment.In recent years, some patents disclose metalloporphyrin bionic catalysis air oxidation hexamethylenes
The technique that alkane prepares adipic acid.As Chinese patent (publication number CN1850756A) and Chinese patent (publication number CN1530358A) are public
Technique and equipment that low-concentration metallic porphyrin bionic catalysis air oxidation of cyclohexane prepares adipic acid are opened, Chinese patent is (open
Number CN1535947A) disclose technique using metalloporphyrin bionic catalysis air oxidation of cyclohexane production adipic acid.But it is sharp
Use air as oxidant the problem is that: oxidation reaction process is the gas-liquid two-phase reaction under high temperature and pressure, and air is from anti-
Tower bottom is answered to enter in kettle, the oxygen of the nitrogen and not fully reacting that are not engaged in oxidation reaction needs in time from reaction tower top
Portion's discharge, and the high-temperature gas discharged will also carry a certain proportion of reaction substrate and product secretly, in this way, the high temperature of reaction kettle discharge
Gas be actually nitrogen, oxygen, reactants and products gaseous mixture.In the industrial production, the high-temperature gas mixture of above-mentioned discharge
It can make most of reactant and production in gaseous mixture by gas-liquid separation tower and condensing tower, and using hypothermic saline forced condensation
Object is recycled, but the gaseous mixture being discharged after condensation and separation still contains micro organic matter and is unable to reach direct emission
Requirement, need to directly adopt combustion system processing, not only energy loss is big, at high cost.Using purity oxygen or oxygen-enriched air generation
For air, it is possible to reduce the volume total amount of gas is discharged, but still not can avoid the discharge of micro-content organism, and due to oxygen
Explosion is easy at high temperature with the mixed gas of hexamethylene and increases the insecurity reacted, therefore now in cyclohexane oxidation
Not using pure oxygen as oxidant in industry, and oxygen source is done using oxygen-enriched or oxygen denuded air, then needed using air and oxygen
Gas is as modulation gas (for oxygen-enriched), or using air and nitrogen as modulation gas (for oxygen deprivation), and oxygen deprivation and oxygen-enriched
Allotment needs two sets of independent devices, and operation is more complicated, at high cost.
Summary of the invention
For existing above-mentioned technical problem during the production adipic acid of air oxidation of cyclohexane in the prior art, the present invention
Purpose be to be to provide a kind of to improve raw material availability and drop during cyclohexane oxidation synthesizing adipic acid using nitrogen circulation
The method of low energy consumption, this method realizes that Organic Ingredients is recycled by designing reasonable nitrogen cycle device, not only environmentally friendly, and
Significant loss is reduced, while realizing low energy consumption, cost is reduced, also improves the control ability of reaction, be conducive to industrialized production.
In order to achieve the above technical purposes, oneself is synthesized two the present invention provides a kind of energy-saving and environment-friendly air oxidation of cyclohexane
The method of acid, this method carry out the reaction that cyclohexane oxidation is converted into adipic acid using nitrogen circulation reaction unit；
The nitrogen circulation reaction unit includes reaction tower, gas-liquid separation tower, condensing tower and air chest；The reaction tower top
Portion is equipped with gas-liquid separation tower, and gas-liquid separation top of tower is equipped with condensing tower, is connect by pipeline with air chest at the top of condensing tower；Distribution
Case is connect by pipeline with reaction tower lower part；Pipeline between condensing tower and air chest is equipped with pressure reducing valve；Air chest with react
Pipeline between tower is equipped with force (forcing) pump；The air chest is equipped with air intake and oxygen intake；
Cyclohexane oxidation synthesizing adipic acid process are as follows: hexamethylene and catalyst mixed raw material are added in reaction tower, and
Heating reaction tower makes temperature in reaction tower reach 140~165 DEG C, while being passed through air, air warp from the air intake of air chest
Be overpressurized pump and be pumped into reaction tower and carry out oxidation reaction with hexamethylene, oxidation reaction residual air pass sequentially through gas-liquid separation tower liquid separation,
After condensing tower condensing recovery organic principle and pressure reducing valve decompression, recycled into air chest；When reaction tower pressure interior force reaches
When 0.8MPa or more, stop being passed through air from air intake, while being passed through oxygen from oxygen intake, to maintain reaction tower pressure interior force
Continue oxidation reaction within the scope of 0.8~1.2MPa, until hexamethylene conversion is complete.
Reaction tower of the invention is suitble to using gas liquid reaction tower or gas-liquid-solid reaction tower common in the art, especially
It is such as to be bubbled gravity reaction tower or stirring using air or oxygen as the gas liquid reaction tower of oxidant or gas-liquid-solid reaction tower
Reaction tower.
Preferred scheme, the condensing tower are that external circulating water-cooled coagulates tower or air setting tower.In the prior art in order to increase
Condensation effect, the organic principle of recycling high-temperature gas entrainment are general using strong cold measure (such as hypothermic saline forced condensation), industry
Equipment requirement is high, at high cost, and energy consumption is high, and technical solution of the present invention is normal using can be directly used after nitrogen circulation technique
The recirculated water or air setting of rule suitably cool down, and have well solved the technical issues of existing strong cold measure is brought.
Preferred scheme, the air chest is interior to be equipped with gas mixer.For example common Wen's mixer of gas mixer.It is logical
Crossing gas mixer can be sufficiently mixed circulating nitrogen gas and the oxygen being filled with uniformly, be conducive to improve the equal of subsequent gas liquid reaction
Even property.
Preferred scheme, the catalyst include transition metal salt and/or metalloporphyrin.
Preferred scheme, when using catalysis of metalloporphyrin agent, the concentration of catalysis of metalloporphyrin agent in the reaction system be 5~
30ppm；Or when using transition metal salt catalyst, the concentration of transition metal salt catalyst in the reaction system is 30~
200ppm；Or when using transition metal salt catalyst and catalysis of metalloporphyrin agent, the concentration of metalloporphyrin in the reaction system
For 5~30ppm, the concentration of transition metal salt in the reaction system is 30~200ppm.
Preferred scheme, the metalloporphyrin include tetraphenylporphyrin iron, four rubigan PORPHYRIN IRONs, tetraphenylporphyrin
Cobalt, Tetraphenyl porphyrin manganese, tetraphenylporphyrin copper, tetraphenylporphyrin iron μ-dimer, four rubigan Cobalt Porphyrins, four rubigan
One or more of Manganese Porphyrin, four rubigan porphyrin coppers, four rubigan PORPHYRIN IRON μ-dimer.
Preferred scheme, the transition metal salt are one of cobalt, manganese, the acetate of copper or naphthenate or several
Kind.
Preferred scheme, reaction time are 60~100min.
Nitrogen circulation reaction unit of the invention is as shown in Figure 1.Main structure includes reaction tower 3, gas-liquid separation tower 4, cold
Solidifying tower 5 and air chest 1.Gas-liquid separation tower is equipped at the top of the reaction tower, gas-liquid separation tower is mainly used for gas-liquid initial gross separation, leads to
It crosses liquid and agglomerates naturally and separated with gas.It is equipped with condensing tower in gas-liquid separation top of tower, condensing tower, will by water cooling or air cooling
The partial organic substances of gas entrainment carry out further condensing recovery.It is connect by pipeline with air chest at the top of condensing tower, after condensation
Gas in be also mingled with a small amount of organic principle, be recycled into air chest, mixed in air chest with the air newly entered.
Air chest is connect by pipeline with reaction tower lower part.Pipeline between condensing tower and air chest is equipped with pressure reducing valve；Air chest with
Pipeline between reaction tower is equipped with force (forcing) pump；Pressure in force (forcing) pump and pressure reducing valve Collaborative Control reaction kettle, and guarantee gas
Smooth circulation.The air chest is equipped with air intake and oxygen intake.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
It is gas liquid reaction during technical solution of the present invention cyclohexane oxidation synthesis of adipic acid, high-temperature reacting gas holds
Easily entrainment organic matter volatilization, is difficult to recycle by general condensation process, not only causes the loss of substrate raw material, and pollute ring
Border, energy loss are big.Technical solution of the present invention realizes that Organic Ingredients is recycled by designing reasonable nitrogen cycle device, no
But it is good for the environment, and reduces significant loss, while realizing low energy consumption, reduce cost, also improve the control ability of reaction,
Technical problem of the existing technology is well solved.The technology of the present invention dexterously carries out nitrogen using nitrogen cycle device
Circulation, on the one hand, in gas-liquid reaction process, can be recycled with the gases by a small amount of organic matter that gas is carried secretly, it is possible to reduce
Significant loss improves raw material availability, and entire reaction process is discharged without exhaust gas, reduces the pollution to environment；On the other hand, gas
In cyclic process, higher recyclegas temperature can be kept, not only need to only be adopted in condensation process without strong cold process
It is all satisfied requirement with condensed water even air setting, the prior art is solved and uses strong cold process device requirement high, it is at low cost
Problem, and the waste heat of high temperature circulation gas is recycled, and reduces the heating energy consumption of reaction kettle, industrial life is greatly saved
Produce cost；The third aspect, the prior art control the gas phase reacted in reaction kettle, mainly by adjusting air, nitrogen and oxygen
The ratio of gas realizes, and after using gas circulation technology, nitrogen circulation is mainly utilized, nitrogen contains in entire reaction system
Amount be it is determining, therefore, the control of gas phase in reaction kettle is only needed to adjust the amount of oxygen being passed through control, therefore, entirely
The control ability of reaction greatly improves, and is conducive to industrialized production.
Detailed description of the invention
Fig. 1 is nitrogen cycle device；
Wherein, 1 is air chest, and 2 be force (forcing) pump, and 3 be reaction tower, and 4 be gas-liquid separation tower, and 5 be condensing tower, and 6 be pressure reducing valve.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention
It encloses.
Embodiment 1
Hexamethylene and tetraphenylporphyrin copper (concentration 20ppm) raw material are added to and are stirred to react in tower, and heats reaction
Tower makes temperature in reaction tower reach 140 DEG C, while being passed through air from the air intake of air chest, and air is pumped into instead by force (forcing) pump
It answers in tower and carries out oxidation reaction with hexamethylene, oxidation reaction residual air passes sequentially through gas-liquid separation tower liquid separation, condensing tower condensing recovery
After organic principle and pressure reducing valve decompression, recycled into air chest；When reaction tower pressure interior force reaches 0.9MPa, stop from air
Entrance is passed through air, while being passed through oxygen from oxygen intake, to maintain reaction tower pressure interior force to continue oxidation instead in 1.2MPa
Answer 90min.Nitrogen circulation reaction unit is not used relatively, by the method in reaction end gas direct emission air, the receipts of adipic acid
Rate improves 3%, and exhaust emissions amount is 0, and energy consumption is substantially reduced.
Embodiment 2
Hexamethylene and cobalt naphthenate (concentration 50ppm) mixed raw material are added to and are bubbled in gravity reaction tower, and is heated
Reaction tower makes temperature in reaction tower reach 160 DEG C, while being passed through air from the air intake of air chest, and air is pumped by force (forcing) pump
Enter and carry out oxidation reaction in reaction tower with hexamethylene, oxidation reaction residual air passes sequentially through gas-liquid separation tower liquid separation, condensing tower condensation
After recycling organic principle and pressure reducing valve decompression, recycled into air chest；When react tower pressure interior force reach 0.8MPa when, stop from
Air intake is passed through air, while being passed through oxygen from oxygen intake, to maintain reaction tower pressure interior force to continue oxygen in 1.0MPa
Change reaction 70min.Nitrogen circulation reaction unit is not used relatively, by the method in reaction end gas direct emission air, adipic acid
Yield improve 5%, exhaust emissions amount is 0, and energy consumption is substantially reduced.
Embodiment 3
Hexamethylene and Tetraphenyl porphyrin manganese (concentration 8ppm) and manganese acetate (concentration 50ppm) mixed raw material are added to
It is stirred to react in tower, and heating reaction tower makes temperature in reaction tower reach 155 DEG C, while being passed through sky from the air intake of air chest
Gas, air are pumped into reaction tower by force (forcing) pump and carry out oxidation reaction with hexamethylene, and oxidation reaction residual air passes sequentially through gas-liquid point
After the decompression of tower liquid separation, condensing tower condensing recovery organic principle and pressure reducing valve, recycled into air chest；When reaction tower pressure interior force
When reaching 0.9MPa, stop being passed through air from air intake, while being passed through oxygen from oxygen intake, to maintain reaction tower pressure interior force
Continue oxidation reaction 70min in 1.2MPa.Nitrogen circulation reaction unit is not used relatively, reaction end gas direct emission is empty
Method in gas, the yield of adipic acid improve 6%, and exhaust emissions amount is 0, and energy consumption is substantially reduced.
Embodiment 4
Hexamethylene and CoTPP (concentration 20ppm) mixed raw material are added to and are stirred to react in tower, and is heated
Reaction tower makes temperature in reaction tower reach 150 DEG C, while being passed through air from the air intake of air chest, and air is pumped by force (forcing) pump
Enter and carry out oxidation reaction in reaction tower with hexamethylene, oxidation reaction residual air passes sequentially through gas-liquid separation tower liquid separation, condensing tower condensation
After recycling organic principle and pressure reducing valve decompression, recycled into air chest；When reaction tower pressure interior force reaches 0.9MPa or more, stop
Only be passed through air from air intake, while being passed through oxygen from oxygen intake, with maintain reaction tower pressure interior force 1.0MPa continue into
Row oxidation reaction 65min.Nitrogen circulation reaction unit is not used relatively, by the method in reaction end gas direct emission air, oneself
The yield of diacid improves 6%, and exhaust emissions amount is 0, and energy consumption is substantially reduced.
Embodiment 5
Hexamethylene and tetraphenylporphyrin iron μ-dimer (concentration 10ppm), cobalt naphthenate (30ppm) mixed raw material are added
Enter into bubbling gravity reaction tower, and heating reaction tower makes temperature in reaction tower reach 150 DEG C, while entering from the air of air chest
Mouth is passed through air, and air is pumped into reaction tower by force (forcing) pump and carries out oxidation reaction with hexamethylene, and oxidation reaction residual air is successively led to
After crossing gas-liquid separation tower liquid separation, condensing tower condensing recovery organic principle and pressure reducing valve decompression, recycled into air chest；Work as reaction
When tower pressure interior force reaches 1MPa or more, stop being passed through air from air intake, while being passed through oxygen from oxygen intake, to remain anti-
Tower pressure interior force is answered to continue oxidation reaction 70min in 1.2MPa.Nitrogen circulation reaction unit is not used relatively, by reaction end gas
Method in direct emission air, the yield of adipic acid improve 7%, and exhaust emissions amount is 0, and energy consumption is substantially reduced.
Embodiment 6
Hexamethylene and Tetraphenyl porphyrin manganese (concentration 20ppm) and manganese naphthenate (150ppm) mixed raw material are added to and are stirred
It mixes in reaction tower, and heating reaction tower makes temperature in reaction tower reach 160 DEG C, while being passed through sky from the air intake of air chest
Gas, air are pumped into reaction tower by force (forcing) pump and carry out oxidation reaction with hexamethylene, and oxidation reaction residual air passes sequentially through gas-liquid point
After the decompression of tower liquid separation, condensing tower condensing recovery organic principle and pressure reducing valve, recycled into air chest；When reaction tower pressure interior force
When reaching 1.1MPa or more, stop being passed through air from air intake, while being passed through oxygen from oxygen intake, to maintain in reaction tower
Pressure continues oxidation reaction 100min in 1.2MPa.Nitrogen circulation reaction unit is not used relatively, reaction end gas is direct
The method in air is discharged, adipic acid improves 7%, and exhaust emissions amount is 0, and energy consumption is substantially reduced.
Embodiment 7
Hexamethylene and Tetraphenyl porphyrin manganese (concentration 15ppm) and tetraphenylporphyrin copper (15ppm) mixed raw material are added
To being stirred to react in tower, and heating reaction tower makes temperature in reaction tower reach 150 DEG C, while being passed through from the air intake of air chest
Air, air are pumped into reaction tower by force (forcing) pump and carry out oxidation reaction with hexamethylene, and oxidation reaction residual air passes sequentially through gas-liquid
After knockout tower liquid separation, condensing tower condensing recovery organic principle and pressure reducing valve decompression, recycled into air chest；When reaction tower internal pressure
When power reaches 1.2MPa or more, stop being passed through air from air intake, while being passed through oxygen from oxygen intake, to maintain reaction tower
Interior pressure continues oxidation reaction 90min in 1.3MPa.Nitrogen circulation reaction unit is not used relatively, reaction end gas is direct
The method in air is discharged, adipic acid improves 8%, and exhaust emissions amount is 0, and energy consumption is substantially reduced.
Embodiment 8
It is anti-that hexamethylene and cobalt acetate (concentration 100ppm) and cobalt naphthenate (100ppm) mixed raw material are added to stirring
It answers in tower, and heating reaction tower makes temperature in reaction tower reach 150 DEG C, while being passed through air from the air intake of air chest, it is empty
Gas is pumped into reaction tower by force (forcing) pump and carries out oxidation reaction with hexamethylene, and oxidation reaction residual air passes sequentially through gas-liquid separation tower point
After liquid, condensing tower condensing recovery organic principle and pressure reducing valve decompression, recycled into air chest；When reaction tower pressure interior force reaches
When 1.2MPa or more, stop being passed through air from air intake, while being passed through oxygen from oxygen intake, to maintain reaction tower pressure interior force
Continue oxidation reaction 90min in 1.2MPa.Nitrogen circulation reaction unit is not used relatively, reaction end gas direct emission is empty
Method in gas, adipic acid improve 7%, and exhaust emissions amount is 0, and energy consumption is substantially reduced.
Embodiment 9
Hexamethylene and four rubigan PORPHYRIN IRON μ-dimer (concentration 20ppm) mixed raw material are added to and are stirred to react
In tower, and heating reaction tower makes temperature in reaction tower reach 140 DEG C, while being passed through air, air from the air intake of air chest
It is pumped into reaction tower by force (forcing) pump and carries out oxidation reaction with hexamethylene, oxidation reaction residual air passes sequentially through gas-liquid separation tower point
After liquid, condensing tower condensing recovery organic principle and pressure reducing valve decompression, recycled into air chest；When reaction tower pressure interior force reaches
When 1.0MPa or more, stop being passed through air from air intake, while being passed through oxygen from oxygen intake, to maintain reaction tower pressure interior force
Continue oxidation reaction 80min in 1.0MPa.Nitrogen circulation reaction unit is not used relatively, reaction end gas direct emission is empty
Method in gas, adipic acid improve 5%, and exhaust emissions amount is 0, and energy consumption is substantially reduced.
Embodiment 10
Hexamethylene and cobalt naphthenate (concentration 200ppm) mixed raw material are added to and are stirred to react in tower, and heats reaction
Tower makes temperature in reaction tower reach 140 DEG C, while being passed through air from the air intake of air chest, and air is pumped into instead by force (forcing) pump
It answers in tower and carries out oxidation reaction with hexamethylene, oxidation reaction residual air passes sequentially through gas-liquid separation tower liquid separation, condensing tower condensing recovery
After organic principle and pressure reducing valve decompression, recycled into air chest；When react tower pressure interior force reach 0.8MPa or more when, stop from
Air intake is passed through air, while being passed through oxygen from oxygen intake, to maintain reaction tower pressure interior force to continue oxygen in 1.0MPa
Change reaction 60min.Nitrogen circulation reaction unit is not used relatively, by the method in reaction end gas direct emission air, adipic acid
4% is improved, exhaust emissions amount is 0, and energy consumption is substantially reduced.
Claims (8)
1. a kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid, it is characterised in that:
The reaction that cyclohexane oxidation is converted into adipic acid is carried out using nitrogen circulation reaction unit；
The nitrogen circulation reaction unit includes reaction tower, gas-liquid separation tower, condensing tower and air chest；It is set at the top of the reaction tower
There is gas-liquid separation tower, gas-liquid separation top of tower is equipped with condensing tower, connect by pipeline with air chest at the top of condensing tower；Air chest is logical
Piping is connect with reaction tower lower part；Pipeline between condensing tower and air chest is equipped with pressure reducing valve；Air chest and reaction tower it
Between pipeline be equipped with force (forcing) pump；The air chest is equipped with air intake and oxygen intake；
Cyclohexane oxidation synthesizing adipic acid process are as follows: hexamethylene and catalyst mixed raw material are added in reaction tower, and heated
Reaction tower makes temperature in reaction tower reach 140~165 DEG C, while being passed through air from the air intake of air chest, and air is by adding
Press pump, which is pumped into reaction tower, carries out oxidation reaction with hexamethylene, and oxidation reaction residual air passes sequentially through gas-liquid separation tower liquid separation, condensation
After tower condensing recovery organic principle and pressure reducing valve decompression, recycled into air chest；When reaction tower pressure interior force reach 0.8MPa with
When upper, stopped from air intake being passed through air, while being passed through oxygen from oxygen intake, with maintain reaction tower pressure interior force 0.8~
Continue oxidation reaction within the scope of 1.2MPa, until hexamethylene conversion is complete.
2. a kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid according to claim 1, feature
Be: the reaction tower is including being bubbled gravity reaction tower or being stirred to react tower.
3. a kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid according to claim 1, feature
Be: the condensing tower is that external circulating water-cooled coagulates tower or air setting tower.
4. a kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid according to claim 1, feature
It is: is equipped with gas mixer in the air chest.
5. a kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid according to claim 1, feature
Be: the catalyst includes transition metal salt and/or metalloporphyrin.
6. a kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid according to claim 1 or 5, special
Sign is: when using catalysis of metalloporphyrin agent, the concentration of catalysis of metalloporphyrin agent in the reaction system is 5~30ppm；Or make
When with transition metal salt catalyst, the concentration of transition metal salt catalyst in the reaction system is 30~200ppm；Or it uses
When transition metal salt catalyst and catalysis of metalloporphyrin agent, the concentration of metalloporphyrin in the reaction system is 5~30ppm, transition
The concentration of metal salt in the reaction system is 30~200ppm.
7. a kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid according to claim 6, feature
Be: the metalloporphyrin includes tetraphenylporphyrin iron, four rubigan PORPHYRIN IRONs, CoTPP, tetraphenylporphyrin
Manganese, tetraphenylporphyrin copper, tetraphenylporphyrin iron μ-dimer, four rubigan Cobalt Porphyrins, four rubigan Manganese Porphyrins, four pairs of chlorine
One or more of phenyl porphyrin copper, four rubigan PORPHYRIN IRON μ-dimer.
8. a kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid according to claim 6, feature
Be: the transition metal salt is one or more of cobalt, manganese, the acetate of copper or naphthenate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2019101396988 | 2019-02-26 | ||
| CN201910139698 | 2019-02-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110128260A true CN110128260A (en) | 2019-08-16 |
Family
ID=67578076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910530479.2A Pending CN110128260A (en) | 2019-02-26 | 2019-06-19 | A kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110128260A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560169A (en) * | 2019-08-19 | 2019-12-13 | 浙江工业大学 | Cycloparaffin catalytic oxidation method promoted by iron porphyrin |
| CN112973727A (en) * | 2019-12-16 | 2021-06-18 | 中国石油天然气股份有限公司 | Catalyst for cyclohexane oxidation, preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106585A (en) * | 1986-09-26 | 1988-06-01 | 三井石油化学工业株式会社 | Process for producing aromatic carboxylic acid |
| CN1115753A (en) * | 1994-03-22 | 1996-01-31 | 三井石油化学工业株式会社 | Process and apparatus for producing aromatic carboxylic acid |
| WO2002000588A1 (en) * | 2000-06-28 | 2002-01-03 | Rhodia Polyamide Intermediates | Method for oxidising hydrocarbons, alcohols and/or ketones |
| CN1535947A (en) * | 2003-04-08 | 2004-10-13 | 湖南大学 | Method of preparing adipic acid by air-oxidating hexacarbocyclic compound |
| CN101088980A (en) * | 2006-06-16 | 2007-12-19 | 兰州瑞德干燥技术有限公司 | Two-stage gas flow-fluidized bed drying process and apparatus with nitogen circulated adipic acid and overheated steam |
| CN101337879A (en) * | 2008-08-18 | 2009-01-07 | 湖南大学 | Process and equipment for preparing adipic acid by catalyzing air and oxidizing cyclohexane |
| CN103755543A (en) * | 2014-01-26 | 2014-04-30 | 沅江华龙催化科技有限公司 | Method for producing adipic acid by oxidizing cyclohexane by utilizing air based on gas-liquid-solid multiphase reaction and separation synchronization reactor |
| CN105085169A (en) * | 2015-09-15 | 2015-11-25 | 沅江华龙催化科技有限公司 | Method for producing KA oil and adipic acid by utilizing air oxidized cyclohexane based on improved reaction-separation synchronous reactor |
| CN207694757U (en) * | 2017-12-05 | 2018-08-07 | 山东海成石化工程设计有限公司 | A kind of butyraldehyde oxidation reaction apparatus of tail gas zero-emission |
-
2019
- 2019-06-19 CN CN201910530479.2A patent/CN110128260A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106585A (en) * | 1986-09-26 | 1988-06-01 | 三井石油化学工业株式会社 | Process for producing aromatic carboxylic acid |
| CN1115753A (en) * | 1994-03-22 | 1996-01-31 | 三井石油化学工业株式会社 | Process and apparatus for producing aromatic carboxylic acid |
| WO2002000588A1 (en) * | 2000-06-28 | 2002-01-03 | Rhodia Polyamide Intermediates | Method for oxidising hydrocarbons, alcohols and/or ketones |
| CN1535947A (en) * | 2003-04-08 | 2004-10-13 | 湖南大学 | Method of preparing adipic acid by air-oxidating hexacarbocyclic compound |
| CN101088980A (en) * | 2006-06-16 | 2007-12-19 | 兰州瑞德干燥技术有限公司 | Two-stage gas flow-fluidized bed drying process and apparatus with nitogen circulated adipic acid and overheated steam |
| CN101337879A (en) * | 2008-08-18 | 2009-01-07 | 湖南大学 | Process and equipment for preparing adipic acid by catalyzing air and oxidizing cyclohexane |
| CN103755543A (en) * | 2014-01-26 | 2014-04-30 | 沅江华龙催化科技有限公司 | Method for producing adipic acid by oxidizing cyclohexane by utilizing air based on gas-liquid-solid multiphase reaction and separation synchronization reactor |
| CN105085169A (en) * | 2015-09-15 | 2015-11-25 | 沅江华龙催化科技有限公司 | Method for producing KA oil and adipic acid by utilizing air oxidized cyclohexane based on improved reaction-separation synchronous reactor |
| CN207694757U (en) * | 2017-12-05 | 2018-08-07 | 山东海成石化工程设计有限公司 | A kind of butyraldehyde oxidation reaction apparatus of tail gas zero-emission |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560169A (en) * | 2019-08-19 | 2019-12-13 | 浙江工业大学 | Cycloparaffin catalytic oxidation method promoted by iron porphyrin |
| CN112973727A (en) * | 2019-12-16 | 2021-06-18 | 中国石油天然气股份有限公司 | Catalyst for cyclohexane oxidation, preparation method and application thereof |
| CN112973727B (en) * | 2019-12-16 | 2023-07-25 | 中国石油天然气股份有限公司 | Catalyst for cyclohexane oxidation, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110204419A (en) | A kind of method of energy-saving and environment-friendly toluene derivative air oxidation synthesizing benzoic alcohol (aldehyde, acid) derivative | |
| CN110128260A (en) | A kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid | |
| CN110105192A (en) | A kind of method of energy-saving and environment-friendly toluene derivative air oxidation synthesizing benzoic acids derivative | |
| CN103755543B (en) | The air oxidation of cyclohexane that utilizes being separated synchronous reaction device based on gas-liquid-solid heterogeneous reaction produces the method for hexanodioic acid | |
| CN109456176A (en) | Novel catalytic oxidation method of cycloparaffin promoted by copper porphyrin | |
| CN113996167B (en) | Process and device for purifying and recycling oxidation reaction tail gas | |
| CN109456175A (en) | New zinc porphyrin promoted cycloparaffin catalytic oxidation method | |
| CN112079702B (en) | Preparation method of chlorobenzaldehyde | |
| CN100591653C (en) | Method for preparing acetic anhydride and acetic acid by multi-component carbonylation | |
| CN113649073A (en) | Method for catalytic oxidation of cycloparaffin by metalloporphyrin bimetallic center 2D MOFs | |
| CN109369327A (en) | Novel nickel porphyrin-promoted cycloparaffin catalytic oxidation method | |
| CN106608865A (en) | Energy-saving method for synthesizing ethylene carbonate | |
| CN110128261A (en) | A kind of method of energy-saving and environment-friendly paraxylene air oxidation synthesis terephthalic acid (TPA) | |
| CN204342435U (en) | The hydrogenation fluidized-bed reactor of anthraquinone legal system hydrogen peroxide | |
| CN109438176A (en) | Novel method for catalytically oxidizing cycloheptane under mild reaction conditions | |
| CN101774999A (en) | Method for synthesizing piperonal | |
| CN110903181B (en) | Method for preparing p-benzoquinone compound by double-catalytic system | |
| CN107522611B (en) | A kind of method that guaiacol prepares formic acid | |
| CN109400480B (en) | Method and equipment for preparing methyl nitrite | |
| CN109608314A (en) | Novel cyclopentane catalytic oxidation method with mild reaction conditions | |
| CN110128255A (en) | A kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesis KA oil | |
| CN109399560A (en) | A method of based on exchange process dissociated methanol | |
| CN111548274A (en) | Method for preparing methyl nitrite by utilizing reaction composite reinforcement | |
| CN104557390A (en) | Method for coproducing and synthesizing liquid methane from methanol purge gas | |
| CN102219679B (en) | Method for producing oxalic acid ester through CO gas phase coupling |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |