CN1308280C - Method for preparing aromatic hydroxyl carboxylic acid - Google Patents
Method for preparing aromatic hydroxyl carboxylic acid Download PDFInfo
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- CN1308280C CN1308280C CNB200410038710XA CN200410038710A CN1308280C CN 1308280 C CN1308280 C CN 1308280C CN B200410038710X A CNB200410038710X A CN B200410038710XA CN 200410038710 A CN200410038710 A CN 200410038710A CN 1308280 C CN1308280 C CN 1308280C
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- aromatic hydroxy
- alkali metal
- metal salt
- reaction
- hydroxy compound
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title abstract description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 title abstract 3
- -1 alkali metal salt Chemical class 0.000 claims abstract description 83
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 14
- ZNYPFGRLOVXIFH-UHFFFAOYSA-N naphthalen-2-ol;sodium Chemical compound [Na].C1=CC=CC2=CC(O)=CC=C21 ZNYPFGRLOVXIFH-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004305 biphenyl Substances 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- 229950011260 betanaphthol Drugs 0.000 claims description 7
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000013459 approach Methods 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 235000011089 carbon dioxide Nutrition 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 5
- 238000007065 Kolbe-Schmitt synthesis reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 239000012053 oil suspension Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Provided is a method for producing an aromatic hydroxycarboxylic acid to proceed with the reaction in high efficiency. The method for the production of an aromatic hydroxycarboxylic acid comprises the reaction of an alkali metal salt of an aromatic hydroxy compound with carbon dioxide in the presence of a medium which is essentially a nonsolvent of the aromatic hydroxy compound alkali metal salt by using a stirrer capable efficiently stirring a liquid independent of the viscosity of the reaction liquid.
Description
[detailed description of the invention]
[technical field that the present invention belongs to]
The present invention relates to method by the prepared in reaction aromatic hydroxy-carboxylic of an alkali metal salt of aromatic hydroxy compound and carbonic acid gas.
[background technology]
Aromatic hydroxy-carboxylic is a kind of broad-spectrum important chemical products, can be by a long time ago with regard to known Kolbe-Schmitt reaction, obtain by an alkali metal salt of aromatic hydroxy compound and carbon dioxide reaction.
For example 2-hydroxyl-3-naphthoic acid is a kind of important compound as the raw material of used charge control agent of the intermediate of pigment, dyestuff and toning agent etc.In addition, right-hydroxy-benzoic acid is as the raw material of the sanitas of macromolecule raw material, makeup and medicine etc., and 2-hydroxyl-6-naphthoic acid all is widely used useful compound as macromolecule raw material, liquid crystalline cpd intermediate.
As the preparation method of aromatic hydroxy-carboxylic, Cole ratio-Shi Mite (コ Le ベ シ ユ ミ Star ト) reaction is at solid and gas mutually down, makes an alkali metal salt and the carbon dioxide reaction of the aromatic hydroxy compound of abundant dehydration, and this is exactly known a long time ago.But, reaction for the solid and gas phase, need the long reaction times, and because the hot unhomogeneity that high temperature reacts down, so it is bigger to have produced the waste that makes as an alkali metal salt of the aromatic hydroxy compound of raw material, be difficult to reaction is controlled owing to phase transformation occurring in the reaction, and be difficult to obtain stable problems such as yield, now proposed various schemes in order to improve this scheme.
An inventor of the present invention uses the liquid reaction of various media to study in the Kolbe-Schmitt reaction that carries out down mutually at solid and gas, and proposes the technology etc. of the improvement that can implement in industry now.
For example, for the method for making of 2-hydroxyl-3-naphthoic acid, invented light oil or kerosene, betanaphthol sodium and the liquid form mixt of Beta Naphthol 99MIN formation and the method (patent documentation 1) of carbon dioxide reaction of making.This method provides a kind of can carry out continuously, and foreign matter content is less, 2-hydroxyl-3-naphthoic acid that the quality deviation is minimum.In addition, the relevant improvement technology of method for making (patent documentation 3) various and the method for making (patent documentation 2) of 2-hydroxyl-6-naphthoic acid, right-hydroxy-benzoic acid has also been proposed.
But the reaction efficiency of Kolbe-Schmitt reaction that adds above-mentioned various innovative approachs is still very low, in addition, has also produced owing to side reaction makes the such problem of material loss.
[patent documentation 1]
Special public clear 56-53296 communique
[patent documentation 2]
Special fair 7-45431 communique
[patent documentation 3]
Special public clear 45-9529 communique
[inventing problem to be solved]
In view of the above problems, the objective of the invention is in the preparation method of aromatic hydroxy-carboxylic, substantially do not dissolve under the existence of medium of an alkali metal salt of aromatic hydroxy compound, an alkali metal salt of aromatic hydroxy compound and the reaction of carbonic acid gas can be carried out effectively.
[solving the method for this problem]
Inventors of the present invention have carried out conscientiously research for the improvement of the industrial making method of aromatic hydroxy-carboxylic, found that, the problem in the background technology results from the viscosity of reaction solution and changes.Just, in Kolbe-Schmitt reaction, the slurries of an alkali metal salt of aromatic hydroxy compound or fused solution etc. is mobile higher when the reaction beginning, but the micro crystal of an alkali metal salt of aromatic hydroxy-carboxylic increases in the reaction system when reaction is carried out, and therefore reacting the later stage becomes full-bodied pasty state.So think because this variation of viscosity reduces reaction efficiency, in addition because heat is inhomogeneous, owing to side reaction makes material loss.
Therefore, found in the operation of reaction,, so far finished the present invention no matter the specific whipping appts that how can stir effectively by the viscosity of using reaction solution can suppress side reaction simultaneously at the improvement reaction efficiency.
That is to say, the present invention relates to a kind of preparation method of aromatic hydroxy-carboxylic, it is characterized in that using the reactor that on the vertically disposed stir shaft of the central part of reactor, has the paddle that the sidewall that carries over reactor and bottom be provided with by the mode of rotating freely, the medium that does not substantially dissolve an alkali metal salt of aromatic hydroxy compound exists down, makes an alkali metal salt and the carbon dioxide reaction of aromatic hydroxy compound.
The reactor that uses among the present invention has stir shaft and paddle, and has following feature as shown in Figure 1.
(1) cross section of reactor 1 is circular, and stir shaft 2 vertically is arranged on its center.
(2) paddle 3 carries over the sidewall 4 of reactor 1 and bottom 5 and is arranged on the stir shaft by the mode of rotating freely.
Paddle preferably adopts anchor formula paddle.
Can have the oar formula paddle 7 of band swept-back wing of the shape of the bottom 5 that carries over reactor 1 in the bottom of paddle 3, in addition, oar formula paddle, hurricane band paddle etc. can be arranged on the top of paddle 3.
The reactor that uses among the present invention can also have baffle plate 6.At this moment, baffle plate 6 rotational trajectory of preferably comparing paddle 3 more approaches the central side of reactor and is provided with.
Baffle plate also can be installed on the sidewall of reactor, can also install from the top of reactor.
The material of the reactor that uses among the present invention, stir shaft, paddle and baffle plate is the material that an alkali metal salt of the aromatic hydroxy compound in the reaction conditions is had erosion resistance, and there is no particular limitation for all the other.For example, can use SUS316L etc. aptly.
As whipping appts, use the NX mixing machine of Japanese chemical machinofacture Co., Ltd. system aptly with this kind paddle and baffle plate.
The reactor that uses among the present invention except having said apparatus, can also have ingress pipe, thermometer stay pipe, pressure warning unit and the vapor pipe etc. of carbon dioxide.
The reactor that has such stirring mechanism by use, substantially do not dissolve under the existence of medium of an alkali metal salt of aromatic hydroxy compound, make an alkali metal salt and the carbon dioxide reaction of aromatic hydroxy compound, can stir effectively to the high viscosity state that reacts the later stage from the low viscosity state of initial reaction stage, can make because the significant loss that side reaction produces reduces, improve reaction yield etc.
Aromatic hydroxy compound in the method for the present invention, preferred phenol or 2-Naphthol, preferred sodium of basic metal or potassium.In addition, as the suitable example of an alkali metal salt of aromatic hydroxy compound, that can enumerate has a betanaphthol sodium.
What the reaction medium of an alkali metal salt that does not dissolve aromatic hydroxy compound in fact that uses among the present invention can be enumerated has, the higher alcohols of high boiling points such as light oil, white oil, kerosene, alkylbenzene, alkylnaphthalene, biphenyl, diphenyl alkane, alkyl biphenyl, terphenyl (triphenyl), hydrogenated terphenyl, diphenyl ether, alkyl phenyl ether, alkyl diphenyl base ether, isooctyl alcohol and their mixture etc.Especially preferably use light oil or hydrogenated terphenyl.
In the preparation method of aromatic hydroxy-carboxylic of the present invention, under the existence for the medium of an alkali metal salt that does not substantially dissolve aromatic hydroxy compound, there is no particular limitation to make an alkali metal salt of aromatic hydroxy compound and the method for carbon dioxide reaction, can use the methods involving of present known Kolbe-Schmitt reaction.As having that the method for be fit to using can be enumerated, for example, in the presence of common, carry out the method for the dehydration procedure of an alkali metal salt of aromatic hydroxy compound and the reaction process of itself and carbonic acid gas etc. with aromatic hydroxy compound; The aromatic hydroxy compound that adds by this method and discharge the outer and method of removing etc. of system by gaseous carbon dioxides in reaction such as secondary aromatic hydroxy compound of giving birth to of reaction and water.
Preparation method for an alkali metal salt of aromatic hydroxy compound that use as reaction raw materials in method for making of the present invention, dehydration has no particular limits.For example, can be in the water knockout that is provided with in addition with reactor, by the alkali metal compound and an alkali metal salt that aromatic hydroxy compound prepares aromatic hydroxy compound of alkali metal hydroxide etc., in the used medium of reaction, heat this salt and dewater.In addition, the reactor that uses among the present invention equally also can prepare an alkali metal salt of the aromatic hydroxy compound of dehydration.
An alkali metal salt of the aromatic hydroxy compound of the dehydration that obtains thus is supplied in the reaction of ensuing and carbonic acid gas.
Preferred 200～350 ℃ of an alkali metal salt of aromatic hydroxy compound and the temperature of reaction of carbonic acid gas, preferred especially 250～300 ℃.If temperature of reaction is lower than 200 ℃, it is low then to have a reaction yield, perhaps needs long problems such as time in order to obtain good yield.If temperature of reaction is higher than 350 ℃, can takes place to reduce, make significant loss make arborescens thing (tar) increase of generation and the problem aspect the quality of the tone of goods, purity etc. etc. owing to produce side reaction owing to an alkali metal salt of the aromatic hydroxy-carboxylic of product can thermolysis makes yield.
Preferred 0.05～the 2MPa of the pressure of carbonic acid gas (G) during reaction, preferred especially 0.2～1MPa (G).
At agitation condition, preferably the circumferential speed at the paddle tip that the formula by paddle diameter (m) * pi * stirring revolution (rpm) ÷ 60 calculates is to carry out under 2～8m/ stirring revolution of second.If most advanced and sophisticated circumferential speed did not then stir fully less than 2m/ second, can not get good yield.If terminal circumferential speed is higher than 8m/ second, then can produce the problem etc. that reaction solution is splashed to the top of responding layer, the expenditure on power that waste is stirred.
Reaction times is according to the difference of the kind of an alkali metal salt of reaction conditions, employed aromatic hydroxy compound and difference is generally 0.5～10 hour, preferred 1～7 hour.
Reaction adds entry stirring, dissolving after finishing the interior composition cooling of afterreaction still.Perhaps can use pump etc. to transfer in the still that is dissolved in water of other setting, then stirring and dissolving.
For an alkali metal salt that makes aromatic hydroxy-carboxylic and since the aromatic hydroxy compound of generations such as by-product or interpolation etc. do not separate out, the temperature of the solution that obtains is remained on 80～100 ℃ state, and separatory is organic layer that is mainly formed by reaction medium and the water layer that contains an alkali metal salt of aromatic hydroxy-carboxylic.
After the water layer that obtains was adjusted to pH6.5～8 by mineral acid etc., the aromatic hydroxy compound that dissociates of an alkali metal salt by the unreacted aromatic hydroxy compound that neutralizes used hydrophobic organic solvent extraction to it.The hydrophobic organic solvent of extraction usefulness uses toluene, dimethylbenzene, oil of mirbane etc. aromatic hydrocarbon based aptly, alcohols such as propyl carbinol, n-Octanol, 2-Ethylhexyl Alcohol, ethers such as dibutyl ether, diphenyl ether, ketones solvents such as pimelinketone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.
From the reaction medium layer and the aromatic hydroxy compound that extracts in the hydrophobic organic solvent by with the aqueous solution of alkali metal hydroxide etc., form with an alkali metal salt of aromatic hydroxy compound extracts, and can be provided with once more using in the reaction after getting back in the dehydration procedure.
The water layer that extracts behind the free aromatic hydroxy compound can be as required, carries out acid out remove the tar class material of tint permanence by the sorbent material of gac etc. after.There is no particular limitation to be used for the acid of acid out, can be by mineral acid, and for example, hydrochloric acid, such diprotic acid, the oxygen acid as sulfuric acid, nitric acid, phosphoric acid, perchloric acid of hydrofluoric acid are adjusted to pH1～3.
The suspension liquid of the aromatic hydroxy-carboxylic that is obtained by acid out separates from mother liquor by usual methods such as centrifugation, press filtrations, as required can through cleaning and refining steps such as recrystallization after, drying obtains product.
The aromatic hydroxy-carboxylic that so obtains is suitable as various uses such as the intermediate of pigment, dyestuff and macromolecule raw material.
[embodiment]
Embodiment 1
At capacity shown in Figure 1 is to add 48% sodium hydroxide, 2-Naphthol in the reaction vessel of 50L, under nitrogen atmosphere, makes 24.9kg (75mol) the 50% betanaphthol sodium aqueous solution.
In this aqueous solution, add light oil, under nitrogen gas stream, be warmed up to 260 ℃, dewater.At this moment,, distilled light oil amount is measured, added light oil at last and make the light oil amount in the reactor be adjusted to 17.4kg because the low boiler cut and the water of light oil are distillated to system together.
After the light oil suspension liquid of the anhydrous betanaphthol sodium that obtains is warmed up to 280 ℃, add 5.4kg (37.5mol) 2-Naphthol.
Then, to make the air pressure of carbonic acid gas be 6.0kg/cm in pressurization
2(G), and be under the condition of 2.7m/ second (stirring revolution 140rpm, paddle footpath 370mm), keep 290 ℃, reacted 1.8 hours in the circumferential speed of paddle end.
After reaction finishes, the immigration of the material in the reactor is equipped with in the dissolving tank of 200L water, under nitrogen atmosphere, temperature is remained on 90 ℃ of dissolvings.Then, in reactor, add the water of 50L, remain on 90 ℃ and clean, washings is transferred in the dissolving tank.
The solution that the washings of reaction soln and reactor is merged remains on 90 ℃, after leaving standstill, is divided into water layer and light oil layer.
Composition to each layer of obtaining is analyzed by high speed liquid chromatography, measures the yield of raw material and product.Its result is as shown in table 1.By analyzing, be benchmark with the betanaphthol sodium, the yield of 2-hydroxyl-3-naphthoic acid is 41.2%, is 8.3% to the transformation efficiency of failing to understand product.
Comparative example 1
Except using the capacity shown in Fig. 2, carry out 1 identical operations with embodiment as the reactor of 50L with outside the terminal circumferential speed of paddle is reacted under as 4.7m/ second (mixing speed 500rpm, paddle footpath 180mm).
By the composition of high speed liquid chromatography analysis water layer and light oil layer, measure the yield of raw material and product.Its result is as shown in table 1.By analyzing, be benchmark with the betanaphthol sodium, the yield of 2-hydroxyl-3-naphthoic acid is 37.7%, betanaphthol sodium is 28.1% to the transformation efficiency of not clear product.
[table 1]
| Last hemistich: yield mole % (is benchmark with the betanaphthol sodium) is hemistich down: output (yield) mole | |||||
| A | B | C | D | E | |
| Embodiment 1 | 41.2 | 0.14 | 0.03 | - | 8.3 |
| 30.9 | 0.11 | 0.02 | 75.2 | 6.2 | |
| Comparative example 1 | 37.7 | 0.21 | 0.05 | - | 28.1 |
| 28.3 | 0.16 | 0.04 | 66.7 | 21.1 | |
A:2-hydroxyl-3-naphthoic acid
B:2-hydroxyl-6-naphthoic acid
C:2-hydroxyl naphthalene-3, the 6-dicarboxylic acid
D: 2-Naphthol and betanaphthol sodium
E: not clear product (from the 2-Naphthol of the betanaphthol sodium of packing into and interpolation, deducting the remaining material of the total amount of A, B, C and D)
Thus, the method according to this invention by reaction solution is carried out competent stirring, can improve the yield of reaction, and suppresses the significant loss that caused by side reaction.
[accompanying drawing summary]
[Fig. 1]
The synoptic diagram of the reactor that uses among the embodiment 1 with the stirring mechanism that uses among the present invention.
[Fig. 2]
The synoptic diagram of the reactor that uses in the comparative example 1 with the stirring mechanism that uses oar formula paddle.
[nomenclature]
1 reactor
2 stir shafts
3 paddles
4 reactor sidewalls
5 reactors bottom
6 baffle plates
The oar formula paddle of 7 band swept-back wings
Claims (5)
1. the preparation method of an aromatic hydroxy-carboxylic, it is characterized in that using and on the vertically disposed stir shaft in the centre of reactor, have the sidewall that carries over reactor and bottom reactor by the paddle that can the mode of rotating freely be provided with, the medium that does not substantially dissolve an alkali metal salt of aromatic hydroxy compound exists down, make an alkali metal salt and the carbon dioxide reaction of aromatic hydroxy compound, wherein paddle is an anchor formula paddle, and this reactor also has baffle plate, and the rotational trajectory that baffle plate is compared paddle more approaches the central side of reactor and is provided with.
2. the preparation method of aromatic hydroxy-carboxylic of record in the claim 1, wherein aromatic hydroxy compound is phenol or 2-Naphthol, basic metal is sodium or potassium.
3. the preparation method of aromatic hydroxy-carboxylic of record in the claim 1, wherein an alkali metal salt of aromatic hydroxy compound is a betanaphthol sodium.
4. the preparation method of aromatic hydroxy-carboxylic of record in the claim 1, the medium that does not wherein dissolve an alkali metal salt of aromatic hydroxy compound in fact is a kind that is selected from light oil, kerosene, white oil, alkylbenzene, alkylnaphthalene, biphenyl, diphenyl alkane, alkyl biphenyl, terphenyl, hydrogenated terphenyl, diphenyl ether, alkyl phenyl ether, alkyl diphenyl base ether, the isooctyl alcohol, perhaps 2 kinds or above mixture.
5. the preparation method of the aromatic hydroxy-carboxylic of record in the claim 1 is characterized in that the most advanced and sophisticated circumferential speed at paddle is under 2～8m/ agitation condition of second, makes an alkali metal salt and the carbon dioxide reaction of aromatic hydroxy compound.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003123805A JP4508548B2 (en) | 2003-04-28 | 2003-04-28 | Process for producing aromatic hydroxycarboxylic acid |
| JP123805/2003 | 2003-04-28 | ||
| JP123805/03 | 2003-04-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1569794A CN1569794A (en) | 2005-01-26 |
| CN1308280C true CN1308280C (en) | 2007-04-04 |
Family
ID=33501592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200410038710XA Expired - Lifetime CN1308280C (en) | 2003-04-28 | 2004-04-28 | Method for preparing aromatic hydroxyl carboxylic acid |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4508548B2 (en) |
| CN (1) | CN1308280C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4934342B2 (en) * | 2006-03-31 | 2012-05-16 | 上野製薬株式会社 | Method for producing 2-hydroxynaphthalene-3,6-dicarboxylic acid |
| CN101654412B (en) * | 2009-09-11 | 2012-07-04 | 四川大学 | Method for preparing 2,7-dicarboxylic-3,6-diacid naphthalinum 3,6-naphthalenedicarboxylate |
| CN103360242A (en) * | 2012-04-09 | 2013-10-23 | 盐城拜克化学工业有限公司 | Preparation method of 6-hydroxy-2-naphthoic acid |
| JP7141303B2 (en) * | 2018-10-15 | 2022-09-22 | 上野製薬株式会社 | Method for producing 5,5'-methylenedisalicylic acid |
| CN113754559A (en) * | 2021-09-14 | 2021-12-07 | 宁波四明化工有限公司 | Method for synthesizing oxime ether |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034362A (en) * | 1988-01-23 | 1989-08-02 | 株式会社上野制药应用研究所 | The preparation method of aromatic hydroxycarboxylic acid |
| WO2000001653A1 (en) * | 1998-07-07 | 2000-01-13 | E.I. Du Pont De Nemours And Company | A process for the isolation of aromatic hydroxycarboxylic acids |
| WO2000003688A1 (en) * | 1998-07-20 | 2000-01-27 | Dentsply International Inc. | Translucent wear resistant dental enamel material and method |
| WO2001019774A1 (en) * | 1999-09-14 | 2001-03-22 | Basf Aktiengesellschaft | Method of producing 2-hydroxycarboxylic acid esters |
| WO2001030741A1 (en) * | 1999-10-23 | 2001-05-03 | Korea Research Institute Of Chemical Technology | Preparing method of alpha-ketocarboxylic acid derivatives |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5123494B1 (en) * | 1974-11-01 | 1976-07-17 |
-
2003
- 2003-04-28 JP JP2003123805A patent/JP4508548B2/en not_active Expired - Lifetime
-
2004
- 2004-04-28 CN CNB200410038710XA patent/CN1308280C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034362A (en) * | 1988-01-23 | 1989-08-02 | 株式会社上野制药应用研究所 | The preparation method of aromatic hydroxycarboxylic acid |
| WO2000001653A1 (en) * | 1998-07-07 | 2000-01-13 | E.I. Du Pont De Nemours And Company | A process for the isolation of aromatic hydroxycarboxylic acids |
| WO2000003688A1 (en) * | 1998-07-20 | 2000-01-27 | Dentsply International Inc. | Translucent wear resistant dental enamel material and method |
| WO2001019774A1 (en) * | 1999-09-14 | 2001-03-22 | Basf Aktiengesellschaft | Method of producing 2-hydroxycarboxylic acid esters |
| WO2001030741A1 (en) * | 1999-10-23 | 2001-05-03 | Korea Research Institute Of Chemical Technology | Preparing method of alpha-ketocarboxylic acid derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004323475A (en) | 2004-11-18 |
| JP4508548B2 (en) | 2010-07-21 |
| CN1569794A (en) | 2005-01-26 |
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