CN1927804A - Method of preparing non-metallic ion 4,5,6-carbon diacid - Google Patents
Method of preparing non-metallic ion 4,5,6-carbon diacid Download PDFInfo
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Abstract
The present invention relates to process of preparing 4, 5, 6-carbo dibasic acid without metal ion. By using washing acid water, which is from the course of preparing cyclohexanol and cyclohexanone via oxidizing cyclohexane with air and contains omega-hydrogen peroxide caproate and other organic matter, as material, and through heating evaporation to concentrate, heating decomposition of omega-hydrogen peroxide caproate at 90-106 deg.c, oxidizing the decomposed product at 40-90 deg.c with 45-68 wt% concentration nitric acid solution to produce mixed solution of 4, 5, 6-carbo dibasic acid, densification, fusing and tabletting, 4, 5, 6-carbo dibasic acid product without metal ion is produced. The present invention has high 4, 5, 6-carbo dibasic acid yield, high conversion rate of organic matter in the washing acid water, no need of high pressure apparatus, simple operation and other advantages.
Description
One, technical field: the preparation method that the present invention relates to a kind of non-metallic ion 4,5,6-carbon dicarboxylic acid, especially a kind of is that raw material produces 4,5, the method for 6-carbon dicarboxylic acid with resulting washing sour water in air oxidation of cyclohexane system hexalin and the pimelinketone technology, belongs to the preparation field of chemical materials.
Two, background technology: in the prior art, the main method of producing hexalin and pimelinketone is to adopt the method for air oxidation of cyclohexane, at first hexanaphthene is not had the catalysis liquid phase air oxidation under certain temperature, pressure and make cyclohexyl hydroperoxide, then cyclohexyl hydroperoxide is carried out catalytic decomposition and obtain hexalin and pimelinketone.In this course, deep oxidation unavoidably takes place in some hexanaphthene, generates some organic acids, ester and other oxidized byproduct, as C
1～C
6Monoprotic acid, C
2～C
6Diprotic acid, ω-hydroxycaproic acid, ω-caproic acid hydrogen peroxide, ester class (as cyclohexyl formate, butyrolactone, caprolactone etc.) and neutrals are (as ortho position, a position and contraposition cyclohexanediol, ortho position, a position or contraposition hexamethylene alcohol ketone, ortho position, a position or contraposition cyclohexenol or cyclonene, valeral, hexanal, ω-hexanal acid etc.) etc.The usually conduct way of these deep oxidation by products is to wash with water, thereby obtains the washing sour water by we are called.
To above-mentioned washing sour water, be to adopt the burning way to handle at first in the industrial production, the result makes not only wherein that organism is wasted, but also has increased processing costs, and production cost is improved accordingly.Another kind of treatment process is to adopt suitable treating processes, and the organism in the washing sour water that obtains is transformed recycling.As U.S. Pat 6,015,924 (the applyings date: 1997-12-12) propose to adopt the method for catalytic hydrogenation, evaporation concentration, nitric acid oxidation to handle this type of washing sour water, be about to wash sour water and send in the hydrogenation reaction kettle of precious metal catalysts such as containing Pt or Pd, be no more than 100 ℃, be no more than make under the hydrogen pressure of 50bar contain in the washing sour water-CH
2OOH ,-CHO ,=C=O ,-hydrogenating reductions such as COOH become alcoholic extract hydroxyl group-CH
2OH or=CHOH, use nitric acid oxidation behind the revaporization concentrating part water, after further handling, can obtain hexanodioic acid and Succinic Acid, pentanedioic acid, hexanodioic acid mixed dibasic acid.The deficiency of this method is: (1) catalytic hydrogenation needs withstand voltage (high pressure) equipment and noble metals such as Pt, Pd to make catalyzer, and production cost is higher; (2) since adopt make that washing sour water Central Plains has behind the shortening-C=O ,-CHO ,-groups such as COOH are reduced into alcoholic extract hydroxyl group, thereby the nitric acid consumption increases when next step uses nitric acid oxidation, in embodiment 1, every acquisition 100g hexanodioic acid, pentanedioic acid, Succinic Acid mixed dibasic acid, needing to drop into concentration is the nitric acid 596g of 58% (weight); (3) mass yield by organism production Succinic Acid, pentanedioic acid, hexanodioic acid mixed dibasic acid in the washing sour water is lower, in embodiment 1, organic content in the former washing sour water is 19.5% (weight), with this washing sour water is raw material production Succinic Acid, pentanedioic acid, hexanodioic acid mixed dibasic acid, every 100g organic content is that the former washing sour water of 19.5% (weight) can obtain the 16.5g mixed dibasic acid, i.e. the ratio of the organism amount in the total amount of gained Succinic Acid, pentanedioic acid, hexanodioic acid and the raw material washing sour water is 0.85.
And for example, the Chinese invention patent ZL 97 1 00669.5 (applying date: 1997-03-11) adopt the method for evaporation concentration, ω-caproic acid hydrogen peroxide decomposition, nitric acid oxidation to handle this type of washing sour water, be that the portion water that first evaporation concentration will be washed in the sour water is removed, again to washing contain in the sour water-CH
2OOH carries out pyrolysis under normal pressure, 90 ℃～104 ℃, or in the presence of catalyzer such as Co or Mn ion, normal pressure, 90 ℃～104 ℃ following cartalytic decomposition effects, make-CH by decomposition reaction
2The OOH decomposition and inversion is alcoholic extract hydroxyl group-CH
2Use nitric acid oxidation behind OH or the aldehyde radical-CHO, after further handling, can obtain hexanodioic acid and Succinic Acid, pentanedioic acid, hexanodioic acid mixed dibasic acid.With U.S. Pat 6,015,924 compare, this method have technical process short, do not need high-tension apparatus, easy and simple to handle, advantage such as the nitric acid consumption is low, but the purity of resulting Succinic Acid, pentanedioic acid, hexanodioic acid mixed dibasic acid is lower, and after obtaining hexanodioic acid and diprotic acid, still there is a certain amount of raffinate to need further to handle, promptly will do not wash organism in the sour water and all be converted into useful products and reclaim.
Three, summary of the invention:
1, goal of the invention: the invention provides a kind of method of producing non-metallic ion 4,5,6-carbon dicarboxylic acid, its objective is the existing method of handling the washing sour water that solves, the not high maybe whole problem of aspect existence such as conversions of organism wherein of its product purity that makes.
2, technical scheme: the present invention is achieved through the following technical solutions:
A kind of non-metallic ion 4 of producing, 5, the method of 6-carbon dicarboxylic acid, it is characterized in that: the washing sour water that this method is produced in hexalin and the pimelinketone process with air oxidation of cyclohexane is a raw material, to wash sour water evaporation concentration under normal pressure or reduced pressure earlier, concentrated solution is at normal pressure, temperature is to carry out ω-caproic acid hydrogen peroxide pyrolysis under 90 ℃～106 ℃ conditions, the mixed solution that obtains after the decomposition carries out oxidizing reaction with 45%～68% nitric acid and generates 4,5, the 6-carbon dicarboxylic acid, oxidation products is enrichment under normal pressure or reduced pressure, fusion, cooling junction plate promptly gets non-metallic ion 4,5,6-carbon dicarboxylic acid product.
The air oxidation of cyclohexane of above-mentioned use is produced the organism that contains weight 15%～25% weight percent in the washing sour water raw material that produces in hexalin and the pimelinketone process, contains the ω-caproic acid hydrogen peroxide of 30%～60% weight percent, the C of 10%～30% weight percent in the organism
2～C
6The C of diprotic acid, 3%～15% weight percent
1～C
6The neutrals of monoprotic acid, 25%～45% weight percent.
Above-mentioned C
1～C
6Monoprotic acid comprises 6 hydroxycaproic acid, hexanal acid; Above-mentioned neutrals is ester class, cyclohexanediol, hexamethylene alcohol ketone, cyclohexenol or cyclonene, aldehydes.
Above-mentioned washing acid evaporation of water is concentrated, its operation control pressure be absolute pressure between 0.060Mpa～0.101Mpa, steam output by volume is 40%～70%, promptly the concentrated solution density scope is controlled at 1.070g/cm
3～1.090g/cm
3(40 ℃), organic content is 40%～55% in the concentrated solution.
It is 55%～65% that steam output by volume measures optimum controling range.
ω-caproic acid hydrogen peroxide is 90 ℃～106 ℃ in normal pressure, temperature and carries out pyrolysis that the content of ω after the decomposition reaction-caproic acid hydrogen peroxide is lower than 2% by weight.
Periodical operation or operate continuously are adopted in the nitric acid oxidation reaction operation.
The nitric acid oxidation reaction time was 1.5h～4.0h when periodical operation was adopted in described nitric acid oxidation reaction operation, and the nitric acid oxidation reaction mean residence time is 4.5h～15.0h when adopting operate continuously; The nitric acid oxidation reaction temperature is 45 ℃～90 ℃, and periodical operation is a gradient increased temperature, and many still series connection are adopted in operate continuously; The oxidizing reaction working pressure is 0.080～0.101Mpa.
Optimum concentration range as the nitric acid of oxygenant is 55%～65% by weight percentage; In anhydride, the quality feed ratio of organism and nitric acid is 1.0: 0.6～1.2 in the decomposed solution.
Oxidation products enrichment, the whole temperature of fusion under 0.050Mpa～0.101Mpa are 140 ℃～180 ℃.
3, advantage and effect: by the enforcement of technical solution of the present invention, can solve the existing method of handling the washing sour water well, it makes the not high problem that maybe aspects such as the whole conversions of organism wherein can not be existed of degree of purity of production.
The present invention is a method of producing non-metallic ion 4,5,6-carbon dicarboxylic acid from air oxidation of cyclohexane system hexalin and pimelinketone process in the washing sour water that contains the caproic acid hydrogen peroxide that produces, thisly produces 4,5, the method for 6-carbon dicarboxylic acid overcome existing preparation method's deficiency.Not only have technical process short, do not need high-tension apparatus, easy and simple to handle, advantage such as the nitric acid consumption is low, simultaneously can obtain highly purified Succinic Acid, pentanedioic acid, hexanodioic acid mixture diprotic acid, and organism is converted into 4,5 in the washing sour water, the mass yield of 6-carbon dicarboxylic acid is higher than 100%, the organic conversion rate of recovery＞98% in the washing sour water.
The present invention has successfully solved the washing sour water that utilizes in air oxidation of cyclohexane production hexalin and the pimelinketone process, mainly contains ω-caproic acid hydrogen peroxide, ω-hydroxycaproic acid, C
4～C
6Organism such as diprotic acid are raw material, produce with the hexanodioic acid be main component 4,5, the processing method of 6-carbon dicarboxylic acid product, its technical process is short, equipment is simple, mixed solution after evaporation concentration and the decomposition reaction is all without separating, directly be used as the raw material of next step reaction, decomposition reaction simultaneously and nitric acid oxidation reaction mild condition, quality product and yield height, the organism rate of recovery of washing in the sour water reaches more than 98%, and 4,5, organic mass ratio is 1.05～1.15 in the quality of 6-carbon dicarboxylic acid product and the washing sour water.When obtaining useful Chemicals, reduced the quantity of wastewater effluent in liquid phase air oxidation hexanaphthene system hexalin and the pimelinketone process widely, reduced environmental pollution significantly, made full use of resource.
Four, embodiment:
The present invention is a kind of method of utilizing the washing sour water that obtains in liquid phase air oxidation hexanaphthene system hexalin and the pimelinketone process to produce non-metallic ion 4,5,6-carbon dicarboxylic acid for raw material, used washing sour water generally contains the organism that mostly is six carbon atom most and accounts for 15%～25% (weight), contains the C of the ω-caproic acid hydrogen peroxide, 10%～30% (weight) of 30%～60% (weight) in the organism
2～C
6The C of diprotic acid, 3%～15% (weight)
1～C
6Monoprotic acid (comprises 6 hydroxycaproic acid, hexanal acid), the neutrals of 20%～40% (weight), in normal pressure or decompression, steam output is that heating evaporation concentrates under 40%～70% (volume) condition, concentrated solution is at normal pressure, temperature is to carry out ω-caproic acid hydrogen peroxide thermolysis between 90 ℃～106 ℃, generally need 4～6h, mixed solution after the decomposition, in temperature is to carry out nitric acid oxidation with 45%～68% nitric acid in 1.0: 0.6～1.2 weight ratios (organism and nitric acid are all with anhydride in the mixed solution) under 40 ℃～90 ℃ conditions, generate hexanodioic acid, pentanedioic acid and Succinic Acid mixed dibasic acid mixed solution, the oxidizing reaction mixed solution is again through the normal pressure enrichment, fusion, the knot sheet promptly gets 4 of non-metallic ion, 5,6-carbon dicarboxylic acid product.
Above-mentioned washing acid evaporation of water is concentrated, its operation control pressure is under 0.060～0.101Mpa (absolute pressure), steam output is 40%～70% (volume), and the steam output optimum controling range is 55%～65% (volume), and promptly the concentrated solution density scope is controlled at 1.070g/cm
3～1.090g/cm
3(40 ℃), organic content is 40%～55% in the concentrated solution.
To the pyrolysis of the ω-caproic acid hydrogen peroxide in the washing sour water evaporation concentration liquid, reaction end is that the content of ω-caproic acid hydrogen peroxide should be lower than 2% (weight).
Mixed solution after the decomposition reaction, when carrying out oxidizing reaction with nitric acid as oxidant, the concentration of nitric acid scope of selecting for use is 45%～68% (weight), its optimum concn is 55%～65% (weight), the oxidizing reaction working pressure is 0.080～0.101Mpa (cutting off), oxidizing reaction temperature is 40 ℃～90 ℃, optimal reaction temperature is 50 ℃～80 ℃, institute's liberated heat is to shift out by the coil heat exchanger in reactor jacket and the reactor in its reaction process, nitric acid oxidation reaction gets final product periodical operation, but also operate continuously, the nitric acid oxidation reaction time is 1.5h～4.0h during periodical operation, the nitric acid oxidation reaction mean residence time is 4.5h～15.0h during operate continuously; In anhydride, the quality feed ratio of organism and nitric acid is 1.0: 0.6～1.2 in the decomposed solution.Every acquisition 100g hexanodioic acid, pentanedioic acid, Succinic Acid mixed dibasic acid, needing to drop into concentration is the nitric acid 170g～200g of 65% (weight), the ratio of organism amount is greater than 1 in the total amount of resulting Succinic Acid, pentanedioic acid, hexanodioic acid and the former washing sour water.
The nitric acid oxidation mixed solution under normal pressure or reduced pressure evaporation concentration to 140 ℃～160 ℃ of temperature of charge, promptly greater than the melt temperature of mixed dibasic acid, can obtain oyster white to non-metallic ion 4,5 yellow-white, flaky, 6-carbon dicarboxylic acid product through cooling junction plate again, the total content of hexanodioic acid, pentanedioic acid and three kinds of diprotic acid of Succinic Acid surpasses 95% (weight) in the product.
Technologies such as above-mentioned evaporation concentration, thermolysis, nitric acid oxidation may be carried out batchwise among the present invention, also can carry out continuously.
Below by embodiment the present invention is carried out more detailed description.
Embodiment 1, embodiment 2, embodiment 3, embodiment 4 used air oxidation of cyclohexane things wash sour water, and wherein organic content is 17.8% (weight), comprises 9.4% (weight) ω-caproic acid hydrogen peroxide.Get the above-mentioned washing sour water of 5000g, under the 0.101Mpa absolute pressure, heating steams the 3000g light constituent, and gained still liquid is concentrated solution, organic content is 42.8% (weight) in the concentrated solution, and this concentrated solution is used for embodiment 1, embodiment 2, embodiment 3, embodiment 4.
Embodiment 5, embodiment 6 used air oxidation of cyclohexane things wash sour water, and wherein organic content is 19.6% (weight), comprises 9.8% (weight) ω-caproic acid hydrogen peroxide.Get the above-mentioned washing sour water of 5000g, under the 0.101Mpa absolute pressure, heating steams the 2900g light constituent, and gained still liquid is concentrated solution, and organic content is 46.6% (weight) in the concentrated solution, and this concentrated solution is used for embodiment 5, embodiment 6.
Embodiment 1:
Get the above-mentioned concentrated solution of 200g, normal pressure heating down carries out decomposition reaction, and control reaction temperature is 95 ℃～100 ℃, reaction 3.5h, and ω in the mixed solution after the decomposition-caproic acid content of hydrogen peroxide is 1.4%.Under constant speed stirred, the mixed solution after will decomposing in 40min added in the nitric acid that 270ml concentration is 65% (weight) and carries out oxidizing reaction, and 50 ℃～60 ℃ of control reaction temperature are warming up to 80 ℃, temperature-rise period time spent 2h after the reinforced end gradually.After oxidizing reaction finishes, the oxidation products mixed solution is carried out evaporation concentration to 160 ℃, with the thin-film evaporator distillation, the distillating mixture of gained is made into laminar, promptly gets 98.2g oyster white, sheet 4,5,6-carbon dicarboxylic acid product then.The total content 95.8% (weight) of hexanodioic acid, pentanedioic acid and three kinds of diprotic acid of Succinic Acid in the product, hexanodioic acid 58.2g, pentanedioic acid 24.2g, Succinic Acid 11.7g in the diprotic acid.
Embodiment 2:
Get the above-mentioned concentrated solution of 300g, normal pressure heating down carries out decomposition reaction, and control reaction temperature is 95 ℃～100 ℃, reaction 4h, and ω in the mixed solution after the decomposition-caproic acid content of hydrogen peroxide is 1.2%.Under constant speed stirred, the mixed solution adding 400ml concentration after will decomposing in 40min was to carry out oxidizing reaction in the nitric acid of 65% (weight), and other operational condition obtains 148g yellowish white, sheet 4,5,6-carbon dicarboxylic acid product with embodiment 1.The total content 96% (weight) of hexanodioic acid, pentanedioic acid and three kinds of diprotic acid of Succinic Acid in the product, hexanodioic acid 87.4g, pentanedioic acid 38.6g, Succinic Acid 16.1g in the diprotic acid.
Embodiment 3:
Get the above-mentioned concentrated solution of 200g, normal pressure heating down carries out decomposition reaction, and control reaction temperature is 98 ℃～104 ℃, reaction 4h, and ω in the mixed solution after the decomposition-caproic acid content of hydrogen peroxide is 1.5%.Under constant speed stirred, the mixed solution adding 280ml concentration after will decomposing in 40min was to carry out oxidizing reaction in the nitric acid of 60% (weight), and other operational condition obtains 98g yellow-white, sheet 4,5,6-carbon dicarboxylic acid product with embodiment 1.The total content 95.6% (weight) of hexanodioic acid, pentanedioic acid and three kinds of diprotic acid of Succinic Acid in the product, hexanodioic acid 60.1g, pentanedioic acid 22.4g, Succinic Acid 11.2g in the diprotic acid.
Embodiment 4:
Get the above-mentioned concentrated solution of 300g, normal pressure heating down carries out decomposition reaction, and control reaction temperature is 98 ℃～104 ℃, reaction 4h, and ω in the mixed solution after the decomposition-caproic acid content of hydrogen peroxide is 1.5%.Under constant speed stirred, the mixed solution adding 438ml concentration after will decomposing in 40min was to carry out oxidizing reaction in the nitric acid of 60% (weight), and other operational condition obtains 149g yellowish white, sheet 4,5,6-carbon dicarboxylic acid product with embodiment 1.The total content 95.9% (weight) of hexanodioic acid, pentanedioic acid and three kinds of diprotic acid of Succinic Acid in the product, hexanodioic acid 86.5g, pentanedioic acid 38.6g, Succinic Acid 17.6g in the diprotic acid.
Embodiment 5:
Get the above-mentioned concentrated solution of 200g, normal pressure heating down carries out decomposition reaction, and control reaction temperature is 95 ℃～100 ℃, reaction 4.5h, and ω in the mixed solution after the decomposition-caproic acid content of hydrogen peroxide is 1.08%.Under constant speed stirred, the mixed solution adding 275ml concentration after will decomposing in 40min was to carry out oxidizing reaction in the nitric acid of 65% (weight), and other operational condition obtains 104g yellow-white, sheet 4,5,6-carbon dicarboxylic acid product with embodiment 1.The total content 96.2% (weight) of hexanodioic acid, pentanedioic acid and three kinds of diprotic acid of Succinic Acid in the product, hexanodioic acid 64.3g, pentanedioic acid 24.2g, Succinic Acid 11.5g in the diprotic acid.
Embodiment 6:
Get the above-mentioned concentrated solution of 300g, do not add catalyzer, normal pressure heating down carries out decomposition reaction, and control reaction temperature is 98 ℃～104 ℃, reaction 5h, and ω in the mixed solution after the decomposition-caproic acid content of hydrogen peroxide is 1.1%.Under constant speed stirred, the mixed solution adding 445ml concentration after will decomposing in 40min was to carry out oxidizing reaction in the nitric acid of 60% (weight), and other operational condition obtains 151g yellowish white, sheet 4,5,6-carbon dicarboxylic acid product with embodiment 1.The total content 95.4% (weight) of hexanodioic acid, pentanedioic acid and three kinds of diprotic acid of Succinic Acid in the product, hexanodioic acid 88.4g, pentanedioic acid 38.2g, Succinic Acid 17.4g in the diprotic acid.
Embodiment 7:
Evaporation concentration, peroxide breakdown and nitric acid oxidation process carry out continuously, and the last handling process of oxidation mixed solution is with embodiment 1.Organic content is 19.8% (weight) in the raw materials used washing sour water, comprises 10.2% (weight) ω-caproic acid hydrogen peroxide; The concentrated solution density that obtains after the washing sour water evaporation concentration is controlled at 1.080～1.085g/cm
3(40 ℃); The content of ω in the peroxide breakdown reaction mixture-caproic acid hydrogen peroxide is controlled at 1%～2% (weight); Nitric acid oxidation reaction is to carry out in the placed in-line stirring tank of three stills, decomposition reaction mixed solution and concentration are that the volume charge ratio of 65% (weight) nitric acid is 3: 2, three stills for air blowing controlled temperature are followed successively by 50 ℃～60 ℃, 60 ℃～70 ℃, 70 ℃～80 ℃, and three still total residence times are 7h.108h has been carried out in operate continuously test, handles raw material washing sour water 16200g, obtains 4,5,6-carbon dicarboxylic acid product 3450g.In the operate continuously process every collection 3h oxidation liquid by embodiment 1 carry out that aftertreatment obtains 4,5,6-carbon dicarboxylic acid product and carry out product quality analysis.The relative content of the total content of product diprotic acid and hexanodioic acid, pentanedioic acid and three kinds of diprotic acid of Succinic Acid sees Table 1.
Embodiment 8:
Evaporation concentration, peroxide breakdown and nitric acid oxidation process carry out continuously, and the last handling process of oxidation mixed solution is with embodiment 1.Organic content is 18.4% (weight) in the raw materials used washing sour water, comprises 9.8% (weight) ω-caproic acid hydrogen peroxide; The concentrated solution density that obtains after the washing sour water evaporation concentration is controlled at 1.080～1.085g/cm
3(40 ℃); The content of ω in the reacted mixed solution of peroxide breakdown-caproic acid hydrogen peroxide is controlled at 1%～2% (weight); Nitric acid oxidation reaction is to carry out in the placed in-line stirring tank of three stills, decomposition reaction mixed solution and concentration are that the volume charge ratio of 60% (weight) nitric acid is 15: 11, three stills for air blowing controlled temperature are followed successively by 50 ℃～60 ℃, 60 ℃～70 ℃, 70 ℃～80 ℃, and three still total residence times are 10h.Other operational conditions are with embodiment 9.117h has been carried out in experiment continuously, handles raw material washing sour water 17020g, obtains 4,5,6-carbon dicarboxylic acid product 3426g.In the operate continuously process every collection 3h oxidation liquid by embodiment 1 carry out that aftertreatment obtains 4,5,6-carbon dicarboxylic acid product and carry out product quality analysis.The relative content of the total content of product diprotic acid and hexanodioic acid, pentanedioic acid and three kinds of diprotic acid of Succinic Acid sees Table 2.
The relative content of table 1 diprotic acid content and hexanodioic acid, pentanedioic acid and Succinic Acid
| Sequence number | Sample time/h | Diprotic acid quality/g | Diprotic acid content/% | Relative content/% | ||
| Succinic Acid | Pentanedioic acid | Hexanodioic acid | ||||
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 | 3 6 9 12 15 18 21 24 27 30 33 36 39 42 45 48 51 54 57 60 63 66 69 72 75 78 81 84 87 90 93 96 99 102 | 95.6 96.0 95.8 95.0 96.2 95.6 95.4 95.8 95.6 95.8 96.1 96.2 95.7 95.2 94.9 95.6 95.9 95.6 96.2 96.2 96.0 96.2 95.8 95.7 95.8 95.6 95.8 95.2 94.9 95.6 95.4 96.2 96.3 96.4 | 96.5 96.4 96.2 96.1 95.9 96.1 95.8 96.0 95.9 95.6 95.6 95.4 95.7 95.9 95.5 95.9 95.4 95.3 95.7 95.5 95.8 95.7 96.3 95.6 95.1 95.9 95.9 95.8 95.4 95.5 95.6 95.9 95.3 95.8 | 12.41 12.18 12.78 12.51 12.81 12.09 12.72 14.01 12.32 12.25 12.17 13.28 12.49 13.07 13.37 13.46 13.03 12.20 12.19 13.88 14.07 12.00 13.13 13.02 12.85 12.31 11.68 13.42 14.76 14.07 13.03 13.37 14.06 12.68 | 28.60 28.91 29.28 29.25 28.33 29.81 28.23 29.52 27.66 27.73 28.11 27.33 27.57 26.93 28.61 27.96 27.98 26.31 26.98 28.80 29.61 27.52 27.18 26.89 26.99 27.92 28.23 28.34 27.57 29.61 27.98 28.61 27.82 26.98 | 58.99 58.91 57.94 58.24 58.86 58.10 59.05 56.47 60.02 60.02 59.72 59.38 59.94 59.99 58.02 58.57 59.04 61.49 60.89 57.32 56.32 60.48 59.69 60.08 60.16 59.77 60.09 58.23 57.68 56.32 59.04 58.02 58.12 60.34 |
| 35 36 | 105 108 | 96.2 96.4 | 96.6 95.6 | 13.58 12.69 | 28.60 29.48 | 57.82 57.83 |
| Add up to | 115 | 3540 | 95.4～ 96.6 | 11.68～ 14.76 | 26.31～ 29.81 | 56.32～ 61.49 |
The relative content of table 2 diprotic acid content and hexanodioic acid, pentanedioic acid and Succinic Acid
| Sequence number | Sample time/h | Diprotic acid quality/g | Diprotic acid content/% | Relative content/% | ||
| Succinic Acid | Pentanedioic acid | Hexanodioic acid | ||||
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 | 3 6 9 12 15 18 21 24 27 30 33 36 39 42 45 48 51 54 57 60 63 66 69 72 75 78 81 84 87 | 87.8 87.6 87.8 87.8 86.9 88.2 88.9 88.8 89.2 89.1 89.2 88.9 88.8 87.8 87.6 87.8 87.8 87.6 87.5 87.6 86.8 86.8 87.6 87.8 87.8 87.6 86.8 86.9 87.6 | 96.3 96.2 96.2 96.5 95.8 96.2 95.8 96.1 95.7 95.6 95.8 95.5 95.3 95.6 95.5 95.6 95.6 95.5 95.3 95.8 95.8 95.5 96.3 95.6 95.4 95.8 95.9 95.8 95.8 | 12.32 12.51 12.41 12.18 12.78 12.51 12.81 12.10 12.72 14.00 12.32 12.28 12.27 13.26 12.49 13.07 13.37 13.46 13.03 12.26 12.19 13.88 14.07 12.00 12.85 13.13 13.02 12.31 13.58 | 28.66 29.25 28.60 28.91 29.28 29.25 28.33 29.80 28.23 29.52 27.62 27.72 28.01 27.36 27.57 26.93 28.61 27.96 27.98 26.28 26.98 28.80 29.61 27.52 26.99 27.18 26.89 27.92 26.89 | 59.02 58.24 58.99 58.91 57.94 58.24 58.86 58.10 59.05 56.48 58.98 60.00 59.72 59.38 59.94 59.99 58.02 58.57 59.04 61.46 60.89 57.32 56.32 60.48 60.16 59.69 60.08 59.77 59.53 |
| 30 31 32 33 34 35 36 37 38 39 | 90 93 96 99 102 105 108 111 114 117 | 87.8 88.2 88.0 87.8 87.6 87.6 88.0 87.6 87.6 87.5 | 95.7 96.1 95.5 95.6 95.9 95.9 95.3 95.8 96.6 95.6 | 11.68 13.42 14.78 14.08 13.07 13.37 14.06 12.88 13.58 12.69 | 28.23 28.34 27.55 29.61 27.98 28.61 27.82 26.98 28.60 29.48 | 60.09 58.23 57.68 56.31 59.00 58.02 58.12 60.14 57.82 57.83 |
| Add up to | 125 | 3426 | 95.3- 96.6 | 11.68- 14.78 | 26.28- 29.80 | 56.31 61.46 |
Claims (10)
1, a kind of non-metallic ion 4 of producing, 5, the method of 6-carbon dicarboxylic acid, it is characterized in that: the washing sour water that this method is produced in hexalin and the pimelinketone process with air oxidation of cyclohexane is a raw material, to wash sour water evaporation concentration under normal pressure or reduced pressure earlier, concentrated solution is at normal pressure, temperature is to carry out ω-caproic acid hydrogen peroxide pyrolysis under 90 ℃～106 ℃ conditions, the mixed solution that obtains after the decomposition carries out oxidizing reaction with 45%～68% nitric acid and generates 4,5, the 6-carbon dicarboxylic acid, oxidation products is enrichment under normal pressure or reduced pressure, fusion, cooling junction plate promptly gets non-metallic ion 4,5,6-carbon dicarboxylic acid product.
2, a kind of method of producing non-metallic ion 4,5,6-carbon dicarboxylic acid according to claim 1, it is characterized in that: the air oxidation of cyclohexane of above-mentioned use is produced the organism that contains weight 15%～25% weight percent in the washing sour water raw material that produces in hexalin and the pimelinketone process, contains the ω-caproic acid hydrogen peroxide of 30%～60% weight percent, the C of 10%～30% weight percent in the organism
2～C
6The C of diprotic acid, 3%～15% weight percent
1～C
6The neutrals of monoprotic acid, 25%～45% weight percent.
3, a kind of method of producing non-metallic ion 4,5,6-carbon dicarboxylic acid according to claim 1 is characterized in that: above-mentioned C
1～C
6Monoprotic acid comprises 6 hydroxycaproic acid, hexanal acid; Above-mentioned neutrals is ester class, cyclohexanediol, hexamethylene alcohol ketone, cyclohexenol or cyclonene, aldehydes.
4, a kind of method of producing non-metallic ion 4,5,6-carbon dicarboxylic acid according to claim 1 and 2, it is characterized in that: above-mentioned washing acid evaporation of water is concentrated, its operation control pressure is that absolute pressure is between 0.060Mpa～0.101Mpa, steam output by volume is 40%～70%, and promptly the concentrated solution density scope is controlled at 1.070g/cm
3～1.090g/cm
3(40 ℃), organic content is 40%～55% in the concentrated solution.
5, a kind of method of producing non-metallic ion 4,5,6-carbon dicarboxylic acid according to claim 4, it is characterized in that: it is 55%～65% that steam output by volume measures optimum controling range.
6, a kind of method of producing non-metallic ion 4,5,6-carbon dicarboxylic acid according to claim 1, it is characterized in that: ω-caproic acid hydrogen peroxide is 90 ℃～106 ℃ in normal pressure, temperature and carries out pyrolysis that the content of ω after the decomposition reaction-caproic acid hydrogen peroxide is lower than 2% by weight.
7, according to claim 1ly a kind ofly obtain 4,5, the method for 6-carbon dicarboxylic acid, it is characterized in that: periodical operation or operate continuously are adopted in the nitric acid oxidation reaction operation.
8, a kind of method of producing non-metallic ion 4,5,6-carbon dicarboxylic acid according to claim 7, it is characterized in that: the nitric acid oxidation reaction time was 1.5h～4.0h when periodical operation was adopted in described nitric acid oxidation reaction operation, and the nitric acid oxidation reaction mean residence time is 4.5h～15.0h when adopting operate continuously; The nitric acid oxidation reaction temperature is 45 ℃～90 ℃, and periodical operation is a gradient increased temperature, and many still series connection are adopted in operate continuously; The oxidizing reaction working pressure is 0.080Mpa～0.101Mpa.
9, according to claim 1 or 8 described a kind of methods of producing non-metallic ion 4,5,6-carbon dicarboxylic acid, it is characterized in that: the optimum concentration range as the nitric acid of oxygenant is 55%～65% by weight percentage; In anhydride, the quality feed ratio of organism and nitric acid is 1.0: 0.6～1.2 in the decomposed solution.
10, a kind of method of producing non-metallic ion 4,5,6-carbon dicarboxylic acid according to claim 1 is characterized in that: oxidation products enrichment, the whole temperature of fusion under 0.050Mpa～0.101Mpa are 140 ℃～180 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936580A (en) * | 2014-03-28 | 2014-07-23 | 北京北化新橡特种材料科技股份有限公司 | Method for obtaining 6-hydroxycaproic acid |
| CN104276937A (en) * | 2014-06-27 | 2015-01-14 | 重庆华峰化工有限公司 | Method for preparing adipic acid and C4-6-dibasic acid from cyclohexane oxidation reaction byproduct |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5741456B2 (en) * | 1973-07-13 | 1982-09-03 | ||
| DE2721858C3 (en) * | 1977-05-14 | 1979-11-08 | Basf Ag, 6700 Ludwigshafen | Process for the production of adipic acid |
| CN1313431C (en) * | 2004-11-26 | 2007-05-02 | 天津大学 | Method of preparing metal ion less adipic acid by nitric acid oxidation of cyclohexane oxidation liquid pickling water |
-
2006
- 2006-09-18 CN CNB2006100477957A patent/CN100450989C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936580A (en) * | 2014-03-28 | 2014-07-23 | 北京北化新橡特种材料科技股份有限公司 | Method for obtaining 6-hydroxycaproic acid |
| CN104276937A (en) * | 2014-06-27 | 2015-01-14 | 重庆华峰化工有限公司 | Method for preparing adipic acid and C4-6-dibasic acid from cyclohexane oxidation reaction byproduct |
| CN104276937B (en) * | 2014-06-27 | 2016-09-28 | 重庆华峰化工有限公司 | Adipic acid and the method for C* binary acid is prepared by cyclohexane oxidation by-product |
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