CN103804161A - Air distribution method in cyclohexane oxidation reaction for cyclohexanone production - Google Patents
Air distribution method in cyclohexane oxidation reaction for cyclohexanone production Download PDFInfo
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- CN103804161A CN103804161A CN201210440039.6A CN201210440039A CN103804161A CN 103804161 A CN103804161 A CN 103804161A CN 201210440039 A CN201210440039 A CN 201210440039A CN 103804161 A CN103804161 A CN 103804161A
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- air
- stills
- oxygen
- oxidation
- air blowing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—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
- C07C45/33—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 of CHx-moieties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention discloses an air distribution method in cyclohexane oxidation reaction for cyclohexanone production. According to the method, seven oxidation kettles are disposed; air is initially introduced into the first oxidation kettle; a lot of process production experiments demonstrate oxygen-rich air is initially introduced into the fourth oxidation kettle; oxygen-rich air is introduced into all the residual oxidation kettles arranged after the fourth oxidation kettles; all the oxidation kettles are connected in series; and the air throughputs of the oxidation kettles increase gradually; The regulation of the throughput of air and oxygen-rich air is realized based on the standard that the oxygen content of tail gas from each oxidation kettle is within a safe range of 2%-3%, and the oxidation conversion rate of cyclohexane in each oxidation kettle is less than 4.5%. When the seven oxidation kettles are in production, oxygen-rich air is introduced, beginning with the fourth oxidation kettle; the selectivity of the whole cyclohexanone oxidation reaction is effectively improved; the reaction system is safe and controllable; and the energy consumption is reduced.
Description
Technical field
The present invention relates to a kind of for the production of the air apportioning method in the cyclohexane oxidation of pimelinketone.
Background technology
In air oxidation of cyclohexane process, hexanaphthene is oxidized to pimelinketone, hexalin, cyclohexyl hydroperoxide, hexanodioic acid etc.Because pimelinketone, hexalin are easier to oxidizedly compared with hexanaphthene, in industrial production, the conversion rate of oxidation of hexanaphthene is controlled at 3.5%～4.0% conventionally, oxidation selectivity 90% left and right, oxidation selectivity refers to that cyclohexane oxidation generates the ratio of target product, and selectivity is better, and output is higher.Although, because low conversion rate is on the low side, there is the shortcomings such as vent gas treatment amount is large, energy consumption is high, facility investment is high in air oxidation of cyclohexane reaction process maturation.Air oxidation of cyclohexane method is produced the throughput of pimelinketone device and is directly determined by the ability to take oxygen of stills for air blowing, and the size of air flow directly determines the output of pimelinketone.But the raising air flow of Complete Infinite degree can cause tail gas to absorb and the load of heat recovery system increases substantially, and tail gas rises containing alkane amount, it (is 18000Nm such as working as air tolerance that device internal recycle hexanaphthene amount rolls up simultaneously
3when/h, the internal circulating load of hexanaphthene 390t/h nearly), form a series of new production bottlenecks.If therefore adopt this method capacity expansion revamping, the improvement cost that causes device increased considerably.By a series of technical study and test, confirm with volume fraction 23%～30%(in order to ensure security, working control value is 23%～25%) oxygen enrichment replaces air produce, strictly control temperature of reaction, pressure, tail gas oxygen level (volume fraction 2%～3%), can expand the throughput of pimelinketone device.Hot research problem both domestic and external with the Study on Process of oxygen enrichment replaces air oxidizing ethyle alkyl always.
At present, prior art has adopted oxygen enrichment to introduce oxidation system, but still there are the following problems, is mainly reflected in following several aspect:
(1) stills for air blowing of domestic current cyclohexane oxidation are all 5 or 7, belong to series connection link flow process, and mostly adopt all stills for air blowing to pass into oxygen enrichment simultaneously, and the participation of too much oxygen can be broken the regularity of distribution of free-radical contents in original air oxidation process after reacting, the free base unit weight that each stills for air blowing produce can change, at the deep oxidation that accelerates cyclohexane oxidation product, when the selectivity that may reduce reaction finally affects pimelinketone output, also may break the balance of whole oxidizing reaction, and even cannot produce the pimelinketone of acceptable quality.
(2) security of reaction system, more oxygen participates in reaction and can cause reaction heat to roll up, and tail gas oxygen level (being called for short tail oxygen) is out of hand, and tail too high oxygen level is brought larger explosive risk to reaction unit;
(3) each stills for air blowing have a minimum air flow, mean that each stills for air blowing have the Schwellenwert of an air capacity.If air flow is very few, can produce pinking, the liquid cyclohexane of stills for air blowing the inside can flow backward in air line and produce burning, and this phenomenon is very dangerous.
Therefore require also will guarantee taking into account under the security of reaction system and the prerequisite of output in controlling oxygen enrichment intake, but which part in technological process starts to pass into oxygen-rich air, and intake control has become the key of oxygen enrichment method production pimelinketone.
Summary of the invention
The object of the present invention is to provide a kind ofly for the production of the air apportioning method in the cyclohexane oxidation of pimelinketone, can effectively promote the selectivity of the oxidizing reaction of whole cyclohexanone, reactive system safety is controlled, has reduced energy consumption simultaneously.
The technical solution used in the present invention is as follows:
A kind of for the production of the air apportioning method in the cyclohexane oxidation of pimelinketone, described method is provided with 7 stills for air blowing, start to pass into air at first stills for air blowing, pass into oxygen-rich air since the 4th stills for air blowing, all stills for air blowing of arranging after described the 4th stills for air blowing all pass into rich gas air, all stills for air blowing are connected in series, and the air flow of stills for air blowing increases step by step;
The regulation and control of the intake of described air and oxygen-rich air, be take oxygen content in each stills for air blowing tail gas out in 2% ~ 3% safety range and the conversion rate of oxidation of the cyclohexane of each stills for air blowing be less than 4.5% as benchmark control.
Oxygen purity in the described oxygen-rich air that passes into stills for air blowing is 23% ~ 25%.
The air flow quantity passing in first three stills for air blowing is respectively 770～780Nm successively
3/ h, 1150～1160Nm
3/ h, 1370～1390Nm
3/ h, the oxygen-rich air flow passing in rear four stills for air blowing is respectively 1760～1775Nm successively
3/ h, 1950～1960Nm
3/ h, 4785～4790Nm
3/ h, 6140～6150Nm
3/ h.
In the time selecting the 4th stills for air blowing to start to pass into oxygen-rich air, the air flow quantity passing in first three stills for air blowing is respectively 775.7Nm successively
3/ h, 1153.3Nm
3/ h, 1380Nm
3/ h, the oxygen-rich air flow passing in rear four stills for air blowing is respectively 1768Nm successively
3/ h, 1955.2Nm
3/ h, 4791.3Nm
3/ h, 6145.4Nm
3/ h.
The oxygen purity of the described oxygen-rich air that passes into stills for air blowing is 23.2%.
The conversion rate of oxidation of described hexanaphthene, is cyclohexane oxidation molar yield %=0.84 × hexalin %+0.8571 × pimelinketone %+0.575 × sour %+0.8129 × ester %+0.7241 × cyclohexyl hydroperoxide %, and its product adopts triphenyl phosphorus method to analyze its content.
Beneficial effect
The present invention is a kind of for the production of the air apportioning method in the cyclohexane oxidation of pimelinketone, by in hexanaphthene reaction process, to after air and pure oxygen mixing, join in stills for air blowing, especially after the explained hereafter experiment by large amount of complex, summary show that at stills for air blowing be 7, select the 4th stills for air blowing to start to pass into oxygen-rich air, can make the selectivity of whole oxidizing reaction higher than the mode that passes into air in stills for air blowing completely, temperature of reaction in reaction process has obtained decline, reactive system safety is controlled, compared with air oxidation process, utilize present method to carry out properly distributed to oxygen-rich air tolerance, can improve the output of pimelinketone, reduced energy consumption simultaneously, thereby reduce production cost, the saving of resource has been played to significant effect.
Accompanying drawing explanation
Fig. 1 is oxygen-rich air and air distribution means figure in cyclohexane oxidation of the present invention;
To be 1 ~ No. 7 stills for air blowing pass into air and oxygen-rich air and whole temperature of reaction comparison diagrams when blowing air by the method in the present invention to Fig. 2;
To be 1 ~ No. 7 stills for air blowing pass into air and oxygen-rich air and whole reaction preference comparison diagrams of blowing airs by the method in the present invention to Fig. 3;
Temperature of reaction comparison diagram when Fig. 4 is 1 ~ No. 7 whole blowing air of stills for air blowing and oxygen-rich air;
Reaction preference comparison diagram when Fig. 5 is 1 ~ No. 7 whole blowing air of stills for air blowing and oxygen-rich air.
Embodiment
In connection with accompanying drawing, the present invention is described in further details:
Fig. 1 is oxygen-rich air and air distribution means figure in cyclohexane oxidation of the present invention, comprise 7 stills for air blowing, 7 stills for air blowing are connected in series, 1 ~ No. 3 stills for air blowing pass into air, 4 ~ No. 7 stills for air blowing pass into oxygen-rich air, are oxygen enrichment dispense station while passing into oxygen-rich air to stills for air blowing at dispense station A, and the valve that dispense station A is connected with 1 ~ No. 3 stills for air blowing is in closing condition, dispense station B passes into air to 1 ~ No. 3 stills for air blowing, passes into hexanaphthene from No. 1 stills for air blowing.
Oxygen by purity 99% is incorporated to air main through excess pressure variable valve, flow control valve, repid cut-off valve after under meter metering; Pressurized air is by certain flow (8000 ~ 18000Nm
3) and pure oxygen proportioning (guarantee oxygen-rich concentration 23 ~ 25%) after enter statical mixer of gases, abundant mixed oxygen-rich air is analyzed oxygen concentration by oxygen concn analyser and is made oxygen level in oxygen-rich air in 23% ~ 25% scope, guarantees the security of reaction unit; Pass into air or oxygen-rich air by setting gasometer to each stills for air blowing, as shown in table 1; Then oxygen-rich air enters through air repid cut-off valve, surge tank is after air dispense station A, pass through respectively the under meter of pipeline separately, according to being undertaken by the tolerance of setting after tolerance metering distributes that oxygen-rich air is transported to stills for air blowing 4 ~ No. 7, now, the valve that dispense station A is connected with 1 ~ No. 3 stills for air blowing keeps closing condition, and the oxygen-rich air that passes into stills for air blowing upwards sprays into from the ring-type distribution piping of each stills for air blowing bottom again, makes oxygen-rich air and hexanaphthene in still, carry out gas liquid reaction.1 ~ 3# stills for air blowing adopt atmospheric oxidation to produce, and pass through after air dispense station B from the air of air compressor, pass through respectively the under meter of pipeline separately, carry out after tolerance metering distributes delivering air to stills for air blowing 1 ~ No. 3 according to the gasometer of setting.
Be 19500Nm in conversion air flow quantity
3when/h, in oxygen-rich air, oxygen purity is 23.2%, under transformation efficiency 3.8% condition, the air flow quantity of setting according to table 1 and oxygen-rich air flow input unit carry out Cyclohexanone Production, compared with all passing into air with all stills for air blowing, it is as shown in table 1 that both plant method temperature of reaction and selectivity in process of production:
The comparison diagram that table 1 temperature of reaction and selectivity and air capacity distribute
The data that obtain from table 1, can obtain 1 ~ No. 7 stills for air blowing and pass into air and oxygen-rich air and whole temperature of reaction comparison diagrams when blowing air by the method in the present invention, as shown in Figure 2; Can also obtain 1 ~ No. 7 stills for air blowing pass into air and oxygen-rich air and whole blowing airs reaction preference comparison diagram by the method in the present invention, as shown in Figure 3 simultaneously.
If 1 ~ No. 7 stills for air blowing all pass into oxygen-rich air, pass into oxygen-rich air according to the oxygen-rich air flow described in table 2 to stills for air blowing, be 17500Nm in conversion air flow quantity
3when/h, in oxygen-rich air, oxygen content is 23.8%, transformation efficiency is the reaction under 3.8%, can obtain 1 ~ No. 7 stills for air blowing and all pass into oxygen-rich air and pass into two kinds of methods of air and carry out Cyclohexanone Production, and both temperature of reaction and selectivity are in process of production as shown in table 2:
Table 2 atmospheric oxidation and oxygen-rich oxide temperature of reaction and selectivity comparison diagram
The data that obtain from table 2, the temperature of reaction can obtain 1 ~ No. 7 stills for air blowing and all pass into oxygen-rich air with whole blowing airs time, as shown in Figure 4; Can also obtain 1 ~ No. 7 stills for air blowing simultaneously and all pass into oxygen-rich air and whole reaction preferencies of blowing airs, as shown in Figure 5.
As seen from Figure 4, guarantee under the consistent prerequisite of output, less when passing into gas gross after oxygen enrichment and comparing pure air; Therefore in the situation that conversion air capacity is equal, all pass into oxygen-rich air in all stills for air blowing, the tail gas amount producing in oxidizing reaction is less, and the heat shifting out in stills for air blowing is less; Therefore compare air oxidation process, oxygen-rich air method requires lower to the feeding temperature of hexanaphthene; Adopt all stills for air blowing all to pass into oxygen-rich air and carry out Cyclohexanone Production, compared with all passing into the production of air method with all stills for air blowing, the temperature entirety of the former oxidizing reaction, all lower than the latter, has been saved steam consumption, and simultaneous reactions temperature reduces the selectivity that is also conducive to improve reaction.
But as can be seen from Table 2, oxygen-rich oxide method 1 ~ 3# stills for air blowing reaction preference is lower than air oxidation process, reason is for guaranteeing each stills for air blowing circulation ratio>=20, and circulation ratio is the characterization parameter of hexanaphthene at the mixed effect of stills for air blowing the inside, to guarantee the circulation mixed effect in stills for air blowing; And, the gas volume that single still passes into must higher than minimum critical tolerance (such as 1,2, the minimum critical tolerance of 3# stills for air blowing is 500Nm
3/ h, 4# stills for air blowing are 800Nm
3/ h, 5# stills for air blowing are 1000Nm
3/ h, 6# stills for air blowing are 2200Nm
3/ h, 7# stills for air blowing are 3800Nm
3/ h), carry out with the safety that guarantees reaction.Under certain tolerance, pass in the oxygen-rich air of 1 ~ 3# stills for air blowing amount of oxygen more than air oxidation process, therefore, oxygen enrichment method is participated in the total oxygen demand of reaction will be more than air method, corresponding single still transformation efficiency, higher than air oxidation process, has reduced the selectivity of oxidizing reaction.The normal condition of above data is the production datas as 3.8%～3.9% time take the conversion rate of oxidation of hexanaphthene, comparison diagram 2 and Fig. 4 can find out, select oxygen-rich air oxidation style to carry out Cyclohexanone Production, distribute in rational situation in tolerance, oxidizing reaction temperature entirety in all stills for air blowing is controlled, does not occur the dangerous phenomenons such as local temperature runaway; Comparison diagram 3 and Fig. 5, can find out and change 1 ~ 3# stills for air blowing into atmospheric oxidation, and 4 ~ No. 7 stills for air blowing are selected oxygen-rich oxide, its reaction preference is produced higher than all pass into oxygen-rich air in 1 ~ No. 7 stills for air blowing, therefore prove that the method for the invention is effective, can solve preferably the safety issue that exists in reaction process and the lower problem of output of pimelinketone.
Claims (5)
1. one kind for the production of the air apportioning method in the cyclohexane oxidation of pimelinketone, it is characterized in that, described method is provided with 7 stills for air blowing, start to pass into air at first stills for air blowing, pass into oxygen-rich air since the 4th stills for air blowing, all stills for air blowing of arranging after described the 4th stills for air blowing all pass into rich gas air, and all stills for air blowing are connected in series, and the air flow of stills for air blowing increases step by step;
The regulation and control of the intake of described air and oxygen-rich air, be take oxygen content in each stills for air blowing tail gas out in 2% ~ 3% safety range and the conversion rate of oxidation of the cyclohexane of each stills for air blowing be less than 4.5% as benchmark control.
2. according to claim 1ly it is characterized in that for the production of the air apportioning method in the cyclohexane oxidation of pimelinketone, described in the oxygen purity that passes in the oxygen-rich air of stills for air blowing be 23% ~ 25%.
According to described in claim 1 or 2 for the production of the air apportioning method in the cyclohexane oxidation of pimelinketone, it is characterized in that, the air flow quantity passing in first three stills for air blowing is respectively 770～780Nm successively
3/ h, 1150～1160Nm
3/ h, 1370～1390Nm
3/ h, the oxygen-rich air flow passing in rear four stills for air blowing is respectively 1760～1775Nm successively
3/ h, 1950～1960Nm
3/ h, 4785～4790Nm
3/ h, 6140～6150Nm
3/ h.
According to described in claim 3 for the production of the air apportioning method in the cyclohexane oxidation of pimelinketone, it is characterized in that, the air flow quantity passing in first three stills for air blowing is respectively 775.7Nm successively
3/ h, 1153.3Nm
3/ h, 1380Nm
3/ h, the oxygen-rich air flow passing in rear four stills for air blowing is respectively 1768Nm successively
3/ h, 1955.2Nm
3/ h, 4791.3Nm
3/ h, 6145.4Nm
3/ h.
5. according to claim 4ly it is characterized in that for the production of the air apportioning method in the cyclohexane oxidation of pimelinketone, described in pass into the oxygen-rich air of stills for air blowing oxygen purity be 23.2%.
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| CN201210440039.6A CN103804161A (en) | 2012-11-06 | 2012-11-06 | Air distribution method in cyclohexane oxidation reaction for cyclohexanone production |
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| CN201210440039.6A CN103804161A (en) | 2012-11-06 | 2012-11-06 | Air distribution method in cyclohexane oxidation reaction for cyclohexanone production |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727228A (en) * | 2017-10-23 | 2018-11-02 | 科迈化工股份有限公司 | A kind of vulcanization accelerator diphenylguanidine（DPG）Continuous production processes |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1932821A1 (en) * | 2006-12-12 | 2008-06-18 | Basf Se | Method for manufacturing oxidation products from Cyclohexan |
| CN101417918A (en) * | 2008-01-08 | 2009-04-29 | 山东洪业化工集团有限公司 | Technique for preparing cyclohexane by benzene hydrogenation using hydrogen produced by oxygen enrichment natural gas steam reforming method |
| CN102000532A (en) * | 2010-10-28 | 2011-04-06 | 中国石油化工股份有限公司 | Cyclohexane oxygen enrichment oxidizing condition kettle air intake method and device thereof |
-
2012
- 2012-11-06 CN CN201210440039.6A patent/CN103804161A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1932821A1 (en) * | 2006-12-12 | 2008-06-18 | Basf Se | Method for manufacturing oxidation products from Cyclohexan |
| CN101417918A (en) * | 2008-01-08 | 2009-04-29 | 山东洪业化工集团有限公司 | Technique for preparing cyclohexane by benzene hydrogenation using hydrogen produced by oxygen enrichment natural gas steam reforming method |
| CN102000532A (en) * | 2010-10-28 | 2011-04-06 | 中国石油化工股份有限公司 | Cyclohexane oxygen enrichment oxidizing condition kettle air intake method and device thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴鑫干等: "环己烷氧化制环己酮工艺及研究进展", 《化工科技》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727228A (en) * | 2017-10-23 | 2018-11-02 | 科迈化工股份有限公司 | A kind of vulcanization accelerator diphenylguanidine（DPG）Continuous production processes |
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Application publication date: 20140521 |