CN1030906A - Method for oxidizing hydrocarbons and equipment - Google Patents
Method for oxidizing hydrocarbons and equipment Download PDFInfo
- Publication number
- CN1030906A CN1030906A CN88104366A CN88104366A CN1030906A CN 1030906 A CN1030906 A CN 1030906A CN 88104366 A CN88104366 A CN 88104366A CN 88104366 A CN88104366 A CN 88104366A CN 1030906 A CN1030906 A CN 1030906A
- Authority
- CN
- China
- Prior art keywords
- arm
- reactor
- baffle plate
- liquid
- reaction solution
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
- C07C27/10—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons
- C07C27/12—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons with oxygen
-
- 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
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
- B01J4/002—Nozzle-type elements
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
- C07C35/08—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring
-
- 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
- B01J2219/00761—Details of the reactor
- B01J2219/00763—Baffles
- B01J2219/00765—Baffles attached to the reactor wall
- B01J2219/00768—Baffles attached to the reactor wall vertical
-
- 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
- B01J2219/18—Details relating to the spatial orientation of the reactor
- B01J2219/182—Details relating to the spatial orientation of the reactor horizontal
-
- 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
- B01J2219/19—Details relating to the geometry of the reactor
- B01J2219/194—Details relating to the geometry of the reactor round
- B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
- B01J2219/1943—Details relating to the geometry of the reactor round circular or disk-shaped cylindrical
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to improve optionally approach of oxidation reactions of hydrocarbons.
Employing contains the method for oxysome oxidizing hydrocarbons, wherein bubbling is entered that the oxic gas of reaction solution is broken for some little airflows in the reactor, with reactor, it is characterized in that adjacent air-flow is distinguished by unaerated to separate.
Hydrocarbon oxidation equipment is made up of the horizontal drum of multistage, each Duan Jun disposes the oxic gas distribution pipe, comprise many porous arms perpendicular to flow direction, distribution pipe upper arm (4) must guarantee not mix mutually from the bubble of alternate arm with the spacing of arm (4), and this spacing must be greater than 400mm.Be provided with baffle plate (6) between arm (4) and arm (4), this baffle plate is immersed under the liquid level and is that free access is left in the reactor bottom top.
Description
The present invention relates to adopt oxygen-containing gas to carry out the method and apparatus of hydro carbons liquid-phase oxidation, thereby improve the selectivity and the coefficient of oxygen utilization of this method.
The liquid-phase oxidation of hydro carbons is the chemical industry common method, and for instance, this method comprises that with cyclohexane oxidation be hexalin or pimelinketone, is isopropyl benzene hydroperoxide with cumene oxidation, is phenylformic acid with toluene oxidation, is terephthalic acid with p xylene oxidation.In the method for oxidation of hexanaphthene, want to reach highly selective and remain in serious problems, promptly required product-hexalin and pimelinketone are easier to be oxidized to by product (being mainly monobasic and di-carboxylic acid) than hexanaphthene self.
Except restriction transformation efficiency this method, another kind can improve hydrocarbon oxidation optionally currently known methods be that its oxidising process is divided into some placed in-line step of reaction, can avoid so-called back mixing like this.In the hydrocarbon oxidation process, the lead-in mode of oxidizing gas is a principal element.The lead-in mode of oxidizing gas should guarantee the suitable extension and the interior turbulent flow that has appropriateness of liquid phase of liquid interface, thereby temperature and/or the concentration avoiding the liquid phase each several part occurring there are differences.
Therefore, oxidizing gas must import reaction liquid from orlop, by adopting perforated bottom, by the porous sparger of ceramal or sintering metal making or by the sparger that the perforated tube that is fit to is made the oxidizing gas bubbling is fed in the reaction solution.For above-mentioned pipe distributor, for instance, be the framework that level is installed, through installing and perforation makes it have perforated bottom and porous sparger, thereby oxic gas is evenly distributed flow and passes through reaction solution with the flow velocity of homogeneous.So the whole liquid on the sparger plane all upwards flow, and has only the downward liquid flow at close reactor wall place outside the sparger horizontal edge.This flow state has hindered the generation of mixing phenomena in the segregation section in the reactor, and this is must pass through very long stretch footpath (along reactor wall or horizontal partition before arrival descends the district because of the liquid that rises.So just, reactor is divided into several sections).This oxic gas lead-in mode can cause the whole depleted of dissolved oxygen, thereby make given section dissolved oxygen and have a large amount of materials not participate in reaction for want of, Another reason is and the contacted reaction solution of oxic gas top dissolved oxygen and the keto consumpting speed of this part is very high no longer.Because the oxygen carrier amount of each section of reactor is a constant, thereby the oxic gas of participating in reaction in certain section can make another section be the situation of oxic gas overload and make the oxygenizement thing in this section oxidized excessively, and promptly required product is oxidized to by product.In the bigger reactor of diameter, on the axle of reactor an additional decline district is arranged, this reactor is horizontal drum, perhaps also disposes the zone parallel with this.
The known device of hydrocarbon oxidation comprises the isolating reactor of several pot types (coupling together by pipeline), or is divided into a reactor of a plurality of conversion zones.For example, disclosed a kind of horizontal drum in polish patent application No64449, wherein by means of several adjacent vertical partition has been divided into several sections with reactor, one of them is an over-pass in every pair of upright partition, and another then separates the vapour space of adjacent segment.Perforated-pipe distributor in these conversion zones is made into frame-like, is imported into reaction solution by the sparger oxic gas.
The reactor of introducing among the Poland Patent No136028 is the deal with problems modified version of scheme of this class.It extends the skeleton construction of pipe distributor, is made up of to similar the cranking arm of reactor bottom curvature many, and they intersect with the reactor axial cross and are connected with the pipe fitting that is parallel to the reaction axle.Improvements are the perforation of distributor arm, and promptly the vertical aperture pitch of arm is greater than the pitch of holes at arm lower central place.This method makes oxic gas flow out evenly along distributor arm, simultaneously, has avoided arm end place air-flow excessively intensive, thereby has avoided the incomplete phenomenon of oxygen absorption to take place.
In the scheme that this is dealt with problems, some puncherless part of distributor arm can also be placed the reactor longitudinal axis, the district thereby acquisition liquid vertically descends, its is in these tops of puncherless section simultaneously again promptly near conversion zone wall.
For selectivity and coefficient of oxygen utilization (promptly reducing the concentration of oxygen in the waste gas) aspect that makes the hydrocarbon oxidation process is further enhanced, the skill in the currently known methods that is adopted is asked and equipment also can be done further improvement.
In the methods of the invention, by finishing the method for using oxygen-containing gas liquid-phase oxidation hydro carbons in the reaction solution through broken air-flow shape oxidizing gas bubbling feeding bubbling reactor, the direction that the bubbling direction and the reaction solution of oxic gas flows through reactor is opposite, and wherein adjacent air-flow is come by the region separation of unaerated.
In the methods of the invention, can drive by the conversion zone import with the oxidation bubble of reaction solution countercurrent flow and flow to the reaction solution of outlet to the upper reaches.And in the unaerated district of reaction solution between bubble flow to following adverse current.Reaction solution contacts with gas once more and is upwards driven again in reactor bottom.Like this, to exporting in this path, reaction solution flows repeatedly up and down by the conversion zone import.This makes reaction solution carry out sufficient multistage circulation on perpendicular to the plane of liquid flow direction.In reaction solution decline zone, replenish fresh oxic gas, the oxygen that is dissolved in hexanaphthene is consumed in reaction, thereby this is reflected under the low oxygen concentration and carries out, and this fact helps optionally improving.Reaction solution can carry out separately around the circulation of carrying out perpendicular to the plane of its flow direction, or being attended by the circulation of carrying out around the plane that is parallel to its flow direction carries out simultaneously.
Hydro carbons liquid-phase oxidation equipment of the present invention is horizontal garden cylindrical drums, and it is divided into plurality of sections and disposes tubular type oxic gas sparger.This sparger is made up of some porous arms perpendicular to liquid flow direction, and especially, the bubble that the spacing arm of sparger must make alternate arm bloat can not mix mutually, and this distance should be greater than 400mm.In order to increase circulation, can adopt circulating baffle plate, be fixed between a certain specific arm and the arm that it parallels.These baffle plates should be immersed in and leave a free access under the liquid level and above reactor bottom.These baffle plates can be configured between the adjacent arm in couples; They just provide separated space for ascending liquid (on the arm) and dropping liq (between the baffle plate) like this.Also can between two alternate arms, only establish a baffle plate: so just ascending liquid and dropping liq are not separated, but still separated the race way that belongs to the sparger particular arm.
The preferred embodiment of the inventive method and equipment is shown in accompanying drawing, and wherein Fig. 1 is the horizontal view in conversion zone longitudinal section; Fig. 2 is the conversion zone cross-sectional plan view.
Embodiment
Adopt the method for air oxidation of cyclohexane under the temperature of the pressure of 0.9 MPa and 160 ℃, to carry out continuously.In order to reach the purpose of this method, must use 130 cubic metres/hour hexanaphthene, the cobalt that 1ppm exists with the cobalt naphthenate form is 5800 cubic metres/hour air as catalyzer and cumulative volume.At a certain specific conversion zone, be with shell wall 1 and partition 2 all around, wherein the liquid level of the reaction solution of Tian Chonging is represented with 3, and air is to enter conversion zone through broken air-flow shape with the direction bubbling opposite with liquid-flow, and this conversion zone is opened with the region separation of no air admission.In the above-mentioned zone that Flow of Goods and Materials arranged, reaction solution and air filled cavity together move upward, and with the zone of the separated no gas flow of aforementioned region in, reaction solution moves downward.Therefore, in being subjected to the reaction solution of oxidizer treatment, can produce the intensive circulation.
This method can be carried out in a horizontal garden cylindricality reactor, and its cumulative volume is 110 cubic metres.6 conversion zones are wherein arranged.Because cyclohexyl hydroperoxide decomposes, except the 6th section, all other conversion zones all dispose oxic gas frame-like pipe distributor, and these spargers are by forming with the vertical tube that is connected with element 5 with the reverse arcuation perforated tube arm 4 of reactor axle.The bubble that the installation of arm 4 must avoid alternate arm to discharge mixes.Its spacing is 450mm.Baffle plate 6 is installed between two arms 4, and this baffle plate immersed in liquid level is following and leave free access for reactor bottom.Oxic gas flows to sparger by axial conduit 7.
Analytical results in the liquid reactor product is a benchmark, and the reaction preference that is converted into hexalin, pimelinketone and cyclohexyl hydroperoxide is 85%.In the oxidising process of hexanaphthene, air bubbling in a known way feeds system, carry out under the condition that oxidising process is constant at temperature and pressure and reactor internal reaction thing is fully loaded, this moment, the cumulative volume and the conversion zone number of reactor were constant, and the reaction preference that is obtained is 82.5%.
Claims (5)
1, adopts the method for oxygen-containing gas liquid-phase oxidation hydro carbons, wherein bubbling is entered that the oxic gas of reaction solution is broken for some little airflows in the reactor, to flow through reactor or conversion zone in the opposite direction, it is characterized in that adjacent logistics is separated by the unaerated differentiation with reaction solution stream.
2, the equipment of liquid-phase oxidation hydro carbons, constitute by a horizontal drum of multistage, all dispose the oxic gas distribution pipe on each section, comprise many porous arms perpendicular to liquid flow direction, the arm (4) that it is characterized in that distribution pipe can not mix from the bubble of alternate arm apart from guaranteeing with arm (4) each interval, and this spacing must be greater than 400mm.
3, according to the described equipment of claim 2, it is characterized in that between arm (4) and arm (4), being provided with circulating baffle plate (6), this baffle plate is immersed under the liquid level and is that free access is left in the reactor bottom top.
4,, it is characterized in that between arm (4) and arm (4), two baffle plates (6) being arranged according to the described equipment of claim 3.
5,, it is characterized in that between arm (4) and arm (4), a baffle plate (8) being arranged according to the described equipment of claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PLP-266877 | 1987-07-15 | ||
| PL1987266877A PL152429B1 (en) | 1987-07-15 | 1987-07-15 | Method of and apparatus for oxydation of hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1030906A true CN1030906A (en) | 1989-02-08 |
| CN1023894C CN1023894C (en) | 1994-03-02 |
Family
ID=20037367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88104366A Expired - Fee Related CN1023894C (en) | 1987-07-15 | 1988-07-15 | Method and apparatus for oxidation of hydrocarbons |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPH0627080B2 (en) |
| KR (1) | KR960016466B1 (en) |
| CN (1) | CN1023894C (en) |
| CS (1) | CS272791B2 (en) |
| DD (1) | DD281803A5 (en) |
| ES (1) | ES2007262A6 (en) |
| PL (1) | PL152429B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101360553B (en) * | 2006-01-04 | 2012-11-14 | 奇派特石化有限公司 | Oxidation system employing internal structure for enhanced hydrodynamics |
| CN106573861A (en) * | 2014-08-08 | 2017-04-19 | 沙特基础工业全球技术有限公司 | Alkylbenzene hydroperoxide production using dispersed bubbles of oxygen containing gas |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL209834B1 (en) * | 2004-02-17 | 2011-10-31 | Zakłady Azotowe W Tarnowie Mościcach Społka Akcyjna | Cyclohexane oxidation reactor and method for oxidation of cyclohexane |
| HUE065168T2 (en) * | 2018-12-26 | 2024-05-28 | Wanhua Chemical Group Co Ltd | Method for oxidizing ethylbenzene |
| CN111471004A (en) * | 2019-01-24 | 2020-07-31 | 中国石化工程建设有限公司 | Preparation method of ethylbenzene hydroperoxide |
-
1987
- 1987-07-15 PL PL1987266877A patent/PL152429B1/en unknown
-
1988
- 1988-07-13 ES ES8802203A patent/ES2007262A6/en not_active Expired
- 1988-07-14 DD DD88317935A patent/DD281803A5/en not_active IP Right Cessation
- 1988-07-14 KR KR1019880008775A patent/KR960016466B1/en not_active IP Right Cessation
- 1988-07-14 JP JP63176195A patent/JPH0627080B2/en not_active Expired - Lifetime
- 1988-07-15 CS CS510988A patent/CS272791B2/en unknown
- 1988-07-15 CN CN88104366A patent/CN1023894C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101360553B (en) * | 2006-01-04 | 2012-11-14 | 奇派特石化有限公司 | Oxidation system employing internal structure for enhanced hydrodynamics |
| CN106573861A (en) * | 2014-08-08 | 2017-04-19 | 沙特基础工业全球技术有限公司 | Alkylbenzene hydroperoxide production using dispersed bubbles of oxygen containing gas |
| CN112250609A (en) * | 2014-08-08 | 2021-01-22 | 沙特基础工业全球技术有限公司 | Alkylbenzene hydroperoxide production using dispersed bubbles of oxygen-containing gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CS272791B2 (en) | 1991-02-12 |
| DD281803A5 (en) | 1990-08-22 |
| JPH0627080B2 (en) | 1994-04-13 |
| ES2007262A6 (en) | 1989-06-01 |
| CN1023894C (en) | 1994-03-02 |
| PL152429B1 (en) | 1990-12-31 |
| KR960016466B1 (en) | 1996-12-12 |
| CS510988A2 (en) | 1990-04-11 |
| KR890001912A (en) | 1989-04-06 |
| JPS6434931A (en) | 1989-02-06 |
| PL266877A1 (en) | 1989-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1085104C (en) | Advanced gas control in gas-liquid mixing system | |
| CA2281398C (en) | Two stage reactor for continuous three phase slurry hydrogenation and method of operation | |
| CN106552560A (en) | A kind of airlift reactor with spiral porous sieve plate | |
| US3847748A (en) | Fermentation method and apparatus | |
| US4207180A (en) | Gas-liquid reaction method and apparatus | |
| US4954257A (en) | Biological purification loop device and method having deflector plate within guide pipe | |
| CN106552577B (en) | A kind of multilayer guide shell bubbling reactor and its application method | |
| EP0264905B1 (en) | Process and apparatus for mixing of gases and liquids | |
| US11628415B2 (en) | Built-in micro interfacial enhanced reaction system and process for PTA production with PX | |
| CN104245075B (en) | Extraction column and process for use thereof | |
| US3642452A (en) | Multistage reactors | |
| KR20130109140A (en) | Methods and apparatus for enhanced gas distribution | |
| CN202785780U (en) | Gas-lift type Fenton oxidizing tower | |
| CN101249405A (en) | Air-lift type circular current reactor | |
| EP3903925A1 (en) | Device and method for oxidizing organic substance | |
| CN206345720U (en) | Nitration denitrification integrated bioreactor | |
| CN1023894C (en) | Method and apparatus for oxidation of hydrocarbons | |
| CN1762570A (en) | Self circulated cascade gas lift type internal-loop reactor system | |
| US3953326A (en) | Oxygen aeration system for contaminated liquids | |
| RU2505524C2 (en) | Reactor of paraxylol oxidation for obtaining terephthalic acid | |
| CN115010258B (en) | Integrated aeration sewage treatment tank for enriching microorganisms in intensive self-circulation manner and construction method thereof | |
| CN217350914U (en) | Self-circulation comprehensive aeration sewage treatment tank | |
| US2886175A (en) | Apparatus for treating a liquid with a gas | |
| RU2147922C1 (en) | Reactor for liquid-phase processes of oxidation of hydrocarbons | |
| CN1313422C (en) | Technology of ion liquid catalyzing benzene and long chain olefin alkylation reaction and its device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |