CN107641078A - A kind of method that propiono Fluidized bed of 2 methyl 6 prepares 2,6 naphthalenedicarboxylic acids - Google Patents
A kind of method that propiono Fluidized bed of 2 methyl 6 prepares 2,6 naphthalenedicarboxylic acids Download PDFInfo
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- CN107641078A CN107641078A CN201711052545.7A CN201711052545A CN107641078A CN 107641078 A CN107641078 A CN 107641078A CN 201711052545 A CN201711052545 A CN 201711052545A CN 107641078 A CN107641078 A CN 107641078A
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Abstract
The invention belongs to technical field of chemical synthesis, and in particular to a kind of method that propiono Fluidized bed of 2 methyl 6 prepares 2,6 naphthalenedicarboxylic acids.This method is to use the propiono naphthalene of 2 methyl 6 as raw material; Co Mn Br series catalysts are used in continuous oxidation reaction device as major catalyst; sylvite, sodium salt or nickel salt are co-catalyst; using one or two kinds of mixtures of glacial acetic acid or propionic acid as solvent; oxygen-containing gas is continuously passed through the propiono naphthalene of 2 methyl of oxidation reactor continuous oxidation 6 and synthesizes 2,6 naphthalenedicarboxylic acids；This method is liquid phase successive reaction, and side reaction is few, and product quality is stable, and technique is simply controllable, can prepare in high yield, the 2 of high-purity, 6 naphthalenedicarboxylic acids.
Description
Technical field
The invention belongs to technical field of chemical synthesis, more particularly to a kind of 2- methyl -6- propionos Fluidized bed prepares 2,6-
The method of naphthalenedicarboxylic acid.
Background technology
NDA is the important monomer for preparing various polyester, polyurethane material and liquid crystal polymer, also extensive
Applied to dyestuff and field of medicaments.NDA structure height is symmetrical, poly- 2, the 6- naphthalenes diformazan obtained with glycol reaction
Diethyl phthalate (PEN), there is the characteristic of straight chain polymer, be the high-performance that a kind of rigidity is good, intensity is big, hot-working character is excellent
Material.PEN is compared with polyethylene terephthalate (PET), PEN heat resistances, barrier, mechanical performance, chemical-resistant resistance
The performances such as property, uviolresistance are more superior；In recent years, market increasingly increases the demand of NDA.But 2,
6- naphthalenedicarboxylic acids production process is complicated, cost is high, and this limits PEN application to a certain extent.Therefore, exploiting economy, height
The NDA synthetic route of effect, it is that domestic and international researcher endeavours research direction.
At present in the method for synthesis NDA, it is research weight that dialkyl group naphthalene liquid phase oxidation, which prepares NDA,
Point, the relevant report of many different catalytic conditions and process engineering has been delivered this both at home and abroad.Wu Zhiqiang, Jin Haibo, Korea Spro account for
The research of the .2,6- diisopropyl naphthalene liquid phase oxidation 2,6- naphthalenedicarboxylic acid catalytic conditions such as raw, petrochemical industry, 2004, (7)
.647-651；Li Daren, Jin Haibo, history peak, petroleum refining and chemical industry, 2006,37 (6)：14-17,2,6-DIPN
Liquid phase oxidation prepares the research of NDA process conditions；Tao Shuaijiang, 2- methyl -6- propiono naphthalene liquid phase oxidations legal system 2,
6- naphthalenedicarboxylic acids, master thesis, 2014；Liu Liang, 2- methyl naphthalene are acylated grinding for oxidation reaction synthesis NDA
Study carefully, master thesis, 2012.The main research work of these documents is, investigated in semicontinuous stirred tank catalyst system and catalyzing and
The research of reaction condition；Oxidation pressure and temperature are high, and reaction time length, yield is in 75-85% or so, subject matter
Gas-liquid mass transfer is bad, and raw material is not reached and is sufficiently mixed in kettle, there is the solvent in addition to acetic acid, reacts for intermittently operated, causes oxygen
Change overreact, the yield of naphthalenedicarboxylic acid product is low；Research prepared by alkyl Fluidized bed, reaction mechanism higher to equipment requirement
Complexity, accessory substance is relatively more, therefore difficulty is also larger.This has resulted in the main original of naphthalenedicarboxylic acid non-large-scale application so far
Cause.
And using 2- methyl naphthalenes as raw material, after the acyl-naphthaline of acylation reaction generation 2- methyl -6, reoxidize to obtain 2,6- naphthalenes two
The synthetic method raw material sources of formic acid are abundant, side reaction is few, product refined easy, and 2,6- are prepared with 2,6- dialkyl group Fluidized bed
The synthetic route of naphthalenedicarboxylic acid is compared to much easier.But research needs HTHP mostly at present, the requirement ratio to equipment
It is higher, high energy consumption, and preferable product yield can not be obtained.
The content of the invention
It is an object of the invention to provide a kind of method that 2- methyl -6- propiono Fluidized beds prepare NDA,
Characterized in that, it the described method comprises the following steps：
(1) be co-catalyst using Co-Mn-Br as catalyst, alkali metal salt or nickel salt, monocarboxylic acid be solvent, with 2- first
Base -6- propiono naphthalene raw materials continuously enter reactor；
(2) using compressed air as oxidant, reactor is continuously fed into the form of bubbling, air is filled with reactant
Tap is touched, and heating response；
(3) reaction solution discharges from bottom overflow, after cooling, after separation of solid and liquid, washing, drying, obtains target product；Point
The mother liquor Returning reactor separated out re-uses.
Step (1) Co-Mn-Br is specially four water cobalt acetates, four water manganese acetates, the mixture of KBr；
Reactor is gas-liquid bubbling type autoclave in the step (1), equipped with condenser, vapour-liquid separator,
Liquid backflow, product separation, drying equipment and compressed-air supply system.
N is first used in the step (1)2Punching press is to 1.0-2.0MPa, reactor pressure during ensureing continuous feed.
Reaction temperature is 160~180 DEG C in the step (2), and it is reaction to maintain reactor temperature during continuous feed
Temperature.
Br in the Co-Mn-Br of the step (1)：Co：Mn mol ratio is (1.4~20)：(1.2~4.0):1, (Co+
Mn)：The mol ratio of 2- methyl -6- propiono naphthalenes is (0.10~0.18):1.
Co-catalyst in the step (1)：(Co+Mn) mol ratio is (1.6~4)：1；The wherein preferred second of alkali metal salt
Sour potassium, sodium acetate, the preferred nickel acetate of nickel salt.
Solvent is the mixture of glacial acetic acid, propionic acid or both, the addition of solvent and rubbing for material quantity in the step (1)
Your ratio is (8-20):1；Appropriate propionic acid is added in solvent can improve the yield of NDA, reduce the inclined benzene three of accessory substance
The amount of acid.
Compressed air and the mol ratio of 2- methyl -6- propiono naphthalenes are (45~60) in the step (2)：1.
Reaction time is 0.5~2h.
After step (3) reaction terminates, the condensed device of reaction vapor, gas-liquid separator, condensate liquid are back to reaction
In device, tail gas empties after processing；Reaction solution discharges from bottom overflow, through cooling, solid- liquid separation, solid phase acetic acid, 50-70
The washing of DEG C hot distilled water is to remove DDGS, through dry NDA solid powder, after the mother liquor isolated, washing
Re-used in acetic acid all Returning reactors.
The product yield obtained through above-mentioned liquid phase successive reaction can reach more than 80%, and mother liquor and solvent after centrifugation
High recycling rate, react again in Returning reactor, obtained product yield is still higher than 80%.
Beneficial effects of the present invention are：
(1) technique provided by the invention, temperature and pressure matches each other according to the vapour pressure of acetic acid, while acetic acid in gas phase
Mole fraction reduce, react and occur to make in the liquid phase reaction at each moment to occur in liquid phase；Reduce acetic acid backflow, suppression
Make because liquid phase very little caused by product colour black, purity reduce phenomenon；Technological reaction temperature is low, effectively can suppress under high temperature
The generation of naphthalene nucleus fracture generation trimellitic acid side reaction.
(2) residence time of technique 2- methyl -6- propiono naphthalenes provided by the invention is appropriate, avoids because overlong time is urged
The problem of agent easily generates complex compound with accessory substance and product purity reduces, and later stage separating-purifying high energy consumption, production cost increase；
, caused intermediate product more the problem of incomplete because aoxidizing is avoided simultaneously.
(3) present invention uses the oxidation reaction that 2- methyl -6- propionos naphthalene is carried out for raw material, and reaction condition is gentle, operation
Easy easily-controllable, raw material sources enrich, accessory substance growing amount is few, can effectively reduce the consumption of lower aliphatic carboxylic acid, avoid excessively
Oxidation, prepare in high yield, the NDA product of high-purity, so as to meet to produce high quality naphthalenedicarboxylic acid second two
The needs of alcohol ester.
Brief description of the drawings
Fig. 1：2- methyl -6- propiono Fluidized beds provided by the invention prepare the process chart of 2,6- naphthalenedicarboxylic acids.
Embodiment
The invention provides a kind of method that 2- methyl -6- propiono Fluidized beds prepare NDA, with reference to
The present invention is described further for drawings and examples.
Embodiment 1
In gas-liquid bubbling stirring autoclave, mixing speed 600r/min, agitating and heating is warming up to 175 DEG C, uses N2
It is pressurized to 1.8MPa；By 120g glacial acetic acids and the water cobalt acetates of 5.80g tetra-, the water manganese acetates of 4.98g tetra-, 7.14g KBrs, 8.58g
Potassium acetate mixed dissolution, is continuously added in reactor by measuring pump；Compressed air is continuously supplied with 3.0 liters of (standard state)/min
Give；72.6g 2- methyl -6- propionos naphthalene is dissolved with 100g glacial acetic acids and continuously supplied by measuring pump, material is put down in reactor
After stopping 2 hours, effuser height in reactor bottom maintains like height with liquid level in reactor, overflow discharging, so may be used
To ensure the solvent and the raw material maintenance reaction that there are abundance in reactor；Reaction solution is after cooling, solid- liquid separation, mother liquor reuse,
Specifically as shown in Figure 1.And the solid separated is washed 2 times with glacial acetic acid, then dried after washing 2 times with 50-70 DEG C of hot distilled water,
Obtain 58.58g khaki solid powders.The purity of NDA and yield are respectively 93.2%, 80.7% after liquid phase analysis.
Comparative example 1.1：Increase the total amount of heavy metal catalyst
By 200g glacial acetic acids and the water cobalt acetates of 8.81g tetra-, the water manganese acetates of 7.46g tetra-, 11.96g KBrs, 15.90g acetic acid
Potassium mixed dissolution, it is continuously added in gas-liquid bubbling reactor；And by 230g glacial acetic acids and 93.34g 2- methyl -6- propiono naphthalenes
Mixed dissolution, it is continuously added to by measuring pump in reactor, the other the same as in Example 1.
76.26g soil white solid powders are obtained after drying, purity and yield through analyzing NDA are respectively
94.0%, 81.7%.
Comparative example 1.2：Increase the total amount of heavy metal catalyst and change co-catalyst
By 500g glacial acetic acids and the water cobalt acetates of 19.15g tetra-, the water manganese acetates of 14.95g tetra-, 11.96g KBrs, 25.90g second
Sour nickel mixed dissolution, is continuously added in gas-liquid bubbling reactor；450g glacial acetic acids and 152.0g2- methyl -6- propiono naphthalenes are mixed
Dissolving is closed, is continuously added to by measuring pump in reactor, the other the same as in Example 1.
126.6g soil white solid powders are obtained after drying, purity and yield through analyzing NDA are respectively
93.8%, 83.3%.
Therefore deduce that, change co-catalyst, and improve the dosage of major catalyst, the yield of target product slightly carries
It is high.
Embodiment 1.3：Recovery centrifugation Mother liquor, solvent
The acetic acid after mother liquor and washing after embodiment 1 is centrifuged as in raw material Returning reactor, be not added with catalyst and
Co-catalyst, other carry out oxidation reaction with embodiment 1；
60.33g khaki solid powders are obtained after drying.The purity of 2,6- naphthalenedicarboxylic acids and yield are respectively after liquid phase analysis
95.6%, 83.1%.
In the mother liquor after using secondary centrifuging and the acetic acid after washing as in raw material Returning reactor, and according to embodiment 1
Middle first time charge proportion supplement 2.28g KBr and 2.0g potassium acetates, and 20g glacial acetic acids, other enter with embodiment 1
Row oxidation reaction；
58.44g khaki solid powders are obtained after drying.The purity of 2,6- naphthalenedicarboxylic acids and yield are respectively after liquid phase analysis
93.4%, 80.5%.
Embodiment 2：
In gas-liquid bubbling stirring autoclave, mixing speed 600r/min, agitating and heating is warming up to 170 DEG C, uses N2
It is pressurized to 1.6MPa；By 200g glacial acetic acids and 50.0g propionic acid and the water cobalt acetates of 9.93g tetra-, the water manganese acetates of 6.73g tetra-, 9.64g bromines
Change potassium, 15.82g potassium acetate mixed dissolutions, be continuously added to by measuring pump in oxidation reactor；Compressed air is with 3.0 liters of (standard shapes
State) in the continuous supplied reactors of/min；260g glacial acetic acids are dissolved with 111.38g 2- methyl -6- propionos naphthalene and connected by measuring pump
Continuous supply, material averagely stop 1 hour in reactor, and effuser height in bottom maintains like height with liquid level in reactor,
Overflow discharges, and can so ensure there is the solvent of abundance and raw material maintenance reaction in reactor；Reaction solution is through cooling, solid-liquid point
From mother liquor reuse.And the solid separated is washed 2 times with glacial acetic acid, then dry, obtain after washing 2 times with 50-70 DEG C of hot distilled water
93.0g soil white solid powders, purity and yield through analyzing NDA are respectively 95.3%, 83.5%.
Comparative example 2.1：Change the amount of solvent propionic acid
By 230g propionic acid and the water cobalt acetates of 8.06g tetra-, the water manganese acetates of 6.62g tetra-, 6.43g KBrs, 11.70g potassium acetates
Mixed dissolution, it is continuously added in oxidation reactor；By 230g glacial acetic acids and 84.0g 2- methyl -6- propiono naphthalene mixed dissolutions,
It is continuously added to by measuring pump in reactor, the other the same as in Example 2.
72.07g soil white solid powders are obtained after drying, purity and yield through analyzing NDA are respectively
98.7%, 85.8%.
It can thus be seen that the addition of solvent propionic acid is advantageous to improve the yield and purity of product.
Embodiment 3：
In gas-liquid bubbling stirring autoclave, mixing speed 600r/min, agitating and heating is warming up to 160 DEG C, uses N2
It is pressurized to 1.0MPa；By 170g glacial acetic acids and the water cobalt acetates of 13.44g tetra-, the water manganese acetates of 6.73g tetra-, 6.43g KBrs,
12.96g potassium acetate mixed dissolutions, are continuously added in oxidation reactor by measuring pump；Compressed air with 3.0 liters (standard state)/
Min is continuously supplied；89.1g 2- methyl -6- propionos naphthalene will be dissolved with 170g glacial acetic acids, it is continuous to supply in oxidation reactor,
After material averagely stops 1.2 hours in reactor, reaction solution is discharged by bottom overflow, after cooling, solid- liquid separation, mother liquor
Reuse.And the solid separated is washed 2 times with glacial acetic acid, then dried after washing 2 times with 50-70 DEG C of hot distilled water, obtain 76.36g soil
White solid powder, purity and yield through analyzing NDA are respectively 96.9%, 85.7%.
Comparative example 3.1：Change reactor types
In gas-liquid bubbling autoclave, by 310g glacial acetic acids and the water cobalt acetates of 13.24g tetra-, the water acetic acid of 6.73g tetra-
Manganese, 6.43g KBrs, 14.50g potassium acetate mixed dissolutions, it is continuously added to by measuring pump in oxidation reactor；With 310g glacial acetic acids
100.3g 2- methyl -6- propionos naphthalene is dissolved and added in reactor, the other the same as in Example 3.
83.25g soil white solid powders are obtained after drying, purity and yield through analyzing NDA are respectively
98.0%, 83.0%.
Claims (9)
1. a kind of method that 2- methyl -6- propiono Fluidized beds prepare NDA, it is characterised in that methods described includes
Following steps：
(1) using Co-Mn-Br mixtures as catalyst, alkali metal salt or nickel salt are co-catalyst, and monocarboxylic acid is solvent, with 2-
Methyl -6- propiono naphthalene raw materials are continuously added to reactor；
(2) air for continuous is fed into reactor, heating response；
(3) reaction solution discharges from bottom overflow, after cooling, after solid- liquid separation, washing, drying, obtains target product；Separation
The mother liquor Returning reactor gone out re-uses；
Step (1) the Co-Mn-Br mixtures are specially four water cobalt acetates, four water manganese acetates, the mixture of KBr.
2. the method that a kind of 2- methyl -6- propiono Fluidized beds according to claim 1 prepare NDA, it is special
Sign is, N is used in the step (1)2Punching press is to 1.0-2.0MPa.
3. the method that a kind of 2- methyl -6- propiono Fluidized beds according to claim 1 prepare NDA, it is special
Sign is that temperature of reactor is 160~180 DEG C in the step (2).
4. the method that a kind of 2- methyl -6- propiono Fluidized beds according to claim 1 prepare NDA, it is special
Sign is, Br in the Co-Mn-Br of the step (1)：Co：Mn mol ratio is (1.4~20)：(1.2~4.0):1, (Co+
Mn)：The mol ratio of 2- methyl -6- propiono naphthalenes is (0.10~0.18):1.
5. the method that a kind of 2- methyl -6- propiono Fluidized beds according to claim 1 prepare NDA, it is special
Sign is, co-catalyst in the step (1)：(Co+Mn) mol ratio is (1.6~4)：1.
6. the method that a kind of 2- methyl -6- propiono Fluidized beds according to claim 1 prepare NDA, it is special
Sign is that solvent is the mixture of glacial acetic acid, propionic acid or both, the addition of solvent and rubbing for material quantity in the step (1)
Your ratio is (8-20):1.
7. the method that a kind of 2- methyl -6- propiono Fluidized beds according to claim 1 prepare NDA, it is special
Sign is that compressed air and 2- methyl -6- propiono naphthalenes mol ratios are (45~60) in the step (2)：1.
8. the method that a kind of 2- methyl -6- propiono Fluidized beds according to claim 1 prepare NDA, it is special
Sign is that the reaction time is 0.5~2h.
9. the method that a kind of 2- methyl -6- propiono Fluidized beds according to claim 1 prepare NDA, it is special
Sign is that separation of solid and liquid described in the step (3) uses centrifugal separation, and the washing uses acetic acid and distilled water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105191A (en) * | 2019-05-28 | 2019-08-09 | 北京石油化工学院 | A method of high-purity naphthalic acid is prepared by raw material of beta-methylnaphthalene |
| CN114832738A (en) * | 2021-08-30 | 2022-08-02 | 煤炭科学技术研究院有限公司 | Reactor with a reactor shell |
| CN115304469A (en) * | 2022-08-19 | 2022-11-08 | 上海沃凯生物技术有限公司 | Synthesis method of 2,6-naphthalenedicarboxylic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4886906A (en) * | 1988-01-11 | 1989-12-12 | Mitsubishi Gas Chemical Company, Inc. | Process for producing 2,6-naphthalene dicarboxylic acid |
| US5110982A (en) * | 1990-01-26 | 1992-05-05 | Mitsubishi Gas Chemical Company, Inc. | Process for producing 2,6-napthalene dicarboxylic acid |
| CN101003475A (en) * | 2007-01-22 | 2007-07-25 | 大连海事大学 | Oxidizing reaction equipment without agitation for preparing aromatic acid |
| CN101244997A (en) * | 2007-02-16 | 2008-08-20 | 北京石油化工学院 | Process for producing 2,6-naphthalenedicarboxylic acid |
| CN101265182A (en) * | 2008-04-23 | 2008-09-17 | 上海红京印实业有限公司 | Method for preparing 2,6-naphthalic acid |
-
2017
- 2017-10-30 CN CN201711052545.7A patent/CN107641078A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4886906A (en) * | 1988-01-11 | 1989-12-12 | Mitsubishi Gas Chemical Company, Inc. | Process for producing 2,6-naphthalene dicarboxylic acid |
| US5110982A (en) * | 1990-01-26 | 1992-05-05 | Mitsubishi Gas Chemical Company, Inc. | Process for producing 2,6-napthalene dicarboxylic acid |
| CN101003475A (en) * | 2007-01-22 | 2007-07-25 | 大连海事大学 | Oxidizing reaction equipment without agitation for preparing aromatic acid |
| CN101244997A (en) * | 2007-02-16 | 2008-08-20 | 北京石油化工学院 | Process for producing 2,6-naphthalenedicarboxylic acid |
| CN101265182A (en) * | 2008-04-23 | 2008-09-17 | 上海红京印实业有限公司 | Method for preparing 2,6-naphthalic acid |
Non-Patent Citations (1)
| Title |
|---|
| 刘亮: "2-甲基萘酰化氧化反应合成2,6-萘二甲酸的研究", 《中国优秀硕士学位论文全文数据库-工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105191A (en) * | 2019-05-28 | 2019-08-09 | 北京石油化工学院 | A method of high-purity naphthalic acid is prepared by raw material of beta-methylnaphthalene |
| CN114832738A (en) * | 2021-08-30 | 2022-08-02 | 煤炭科学技术研究院有限公司 | Reactor with a reactor shell |
| CN115304469A (en) * | 2022-08-19 | 2022-11-08 | 上海沃凯生物技术有限公司 | Synthesis method of 2,6-naphthalenedicarboxylic acid |
| CN115304469B (en) * | 2022-08-19 | 2024-03-29 | 上海沃凯生物技术有限公司 | Synthesis method of 2, 6-naphthalene dicarboxylic acid |
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