CN100545083C - A kind of hydroxylamine-oximation circulatoing system - Google Patents
A kind of hydroxylamine-oximation circulatoing system Download PDFInfo
- Publication number
- CN100545083C CN100545083C CNB2007100006864A CN200710000686A CN100545083C CN 100545083 C CN100545083 C CN 100545083C CN B2007100006864 A CNB2007100006864 A CN B2007100006864A CN 200710000686 A CN200710000686 A CN 200710000686A CN 100545083 C CN100545083 C CN 100545083C
- Authority
- CN
- China
- Prior art keywords
- treating liquid
- inorganic treating
- azanol
- oximation
- tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
A kind of hydroxylamine-oximation circulatoing system comprises: (a) azanol reaction district; (b) oximation reaction district; (c) purifying area; And the adjustment district that (d) has nitric acid absorption tower, the employed inorganic treating liquid of this reactive system only partly enters nitric acid absorption tower and replenishes nitrate ion in this adjustment district, mix with remaining inorganic treating liquid again after adjusting composition, thereby the azanol that can reduce in this inorganic treating liquid destroys the ratio of losing because of decomposition.Moreover the purifying area of this system can be removed the high boiling point organic pollutant in the inorganic treating liquid effectively, avoids poisoning the employed catalyzer of azanol reaction, and reduces the selection rate of activity of such catalysts and azanol reaction, more helps making the high density azanol.
Description
Technical field
The present invention relates to a kind of hydroxylamine-oximation circulatoing system, particularly relate to a kind of hydroxylamine-oximation circulatoing system of making the high-concentration phosphoric acid azanol.
Background technology
The manufacturing of industrial relevant azanol normally recycles in conjunction with other processing mode, hydroxylamine-oximation circulatoing system for example, be exactly as inorganic treating liquid with phosphoric acid salt, with nitric acid, hydrogen is that raw material becomes azanol with nitrate reduction under catalyst, and formed azanol carries out oximation reaction with pimelinketone again and forms cyclohexanone-oxime.Phosphoric acid salt inorganic treating liquid behind the oximation reaction adds nitric acid again or the absorption nitrous gases forms nitric acid, to increase the content of needed nitrate ion, enters hydroxylamine reactor again and prepares azanol, and its reaction is shown below:
Azanol reaction is made phosphatic hydroxylamine
NH
4NO
3+2H
3PO
4+3H
2→NH
3OH.H
2PO
4+NH
4H
2PO
4+2H
2O
Oximation reaction is made cyclohexanone-oxime
NH
3OH.H
2PO
4+C
6H
10O→C
6H
10NOH+H
2O+H
3PO
4
Replenish the nitrate ion of phosphoric acid salt inorganic treating liquid
HNO
3+H
2PO
4 -→NO
3 -+H
3PO
4
Fig. 1 is the synoptic diagram of general azanol-oximate circular treatment, includes hydroxylamine reactor (10), Oximation tower (30), extraction tower (50), stripping tower (70) and nitric acid absorption tower (90).The inorganic treating liquid and the hydrogen that contain nitrate ion are fed to the synthetic phosphatic hydroxylamine of hydroxylamine reactor (10) via pipeline 101,103 respectively, and unreacted hydrogen and other gas are discharged by pipeline 105.The inorganic treating liquid that contains phosphatic hydroxylamine through pipeline 107 by its top feed to Oximation tower (30), the organic phase reaction solution system of containing pimelinketone imports Oximation tower (30) through pipeline 113,115 by the bottom, oximation reaction is carried out in contact under adverse current.The organic phase that contains cyclohexanone-oxime from Oximation tower (30) top via pipeline 117 overflow dischargings, remaining phosphoric acid salt inorganic treating liquid from Oximation tower (30) bottom via pipeline 119 dischargings.Enter extraction tower (50) from the phosphoric acid salt inorganic treating liquid of Oximation tower (30) bottom discharge by pipeline 119, remove remaining cyclohexanone-oxime.Then, send into stripping tower (70), carry out stripping, further remove remaining organic pollutant via pipeline 125.At last, send into the content that nitric acid absorption tower (90) replenishes nitrate ion, re-circulate to the synthetic phosphatic hydroxylamine of hydroxylamine reactor through pipeline 129.
In this hydroxylamine-oximation circulatoing system, after azanol and pimelinketone are finished oximation reaction, separate the inorganic treating liquid of discharging by the oximation reaction device, the residual organic pollutant of meeting, and be unfavorable for the whole recycle system.At first, the organic pollutant in the inorganic treating liquid can produce the catalyzer of azanol reaction and poison, and causes the active and optionally reduction of catalyst reaction, causes azanol concentration and output to be restricted and can't to promote.Moreover when the inorganic treating liquid of residual organic pollutant entered nitric acid absorption tower, the waste gas that is given off caused the corrosion of contact material easily.Therefore, how to reduce the organic pollutant content in the inorganic treating liquid, become the key factor of making the high density azanol.
The U.S. the 3rd, 997, No. 607 patent disclosures a kind of heat-treating methods that utilizes, reduce the organic pollutant content in the inorganic treating liquid.Yet the waste gas that is given off in this kind heat treatment process causes the corrosion of contact material easily.Moreover, improve heat treated temperature as desire, further reduce the total content of organic carbon in the inorganic treating liquid, then may make organism generation condensation reaction cause the yellow of inorganic treating liquid color, make remaining organic pollutant be difficult for more removing, and be unfavorable for W-response.
On the other hand, this inorganic treating liquid enters nitric acid absorption tower and replenishes in the process of nitrate ion, and the micro-azanol in this inorganic treating liquid can go to pot because of decomposition.Therefore, for the hydroxylamine-oximation circulatoing system that uses high-concentration phosphoric acid azanol manufacturing cyclohexanone-oxime, still need a kind of organism of more effectively removing in the inorganic treating liquid to avoid the micro-azanol in this inorganic treating liquid to destroy damnous method simultaneously because of decomposition.
Summary of the invention
The object of the present invention is to provide a kind of hydroxylamine-oximation circulatoing system of making the high density azanol.
Another object of the present invention is to provide a kind of hydroxylamine-oximation circulatoing system that can reduce the organic content in the inorganic treating liquid.
Another purpose of the present invention is to provide a kind of azanol that can reduce in the inorganic treating liquid to destroy the hydroxylamine-oximation circulatoing system that loses because of decomposing.
For reaching above-mentioned and other purpose, the invention provides a kind of hydroxylamine-oximation circulatoing system, comprising: (a) azanol reaction district, in order in containing the inorganic treating liquid of acid buffer agent, under the condition that catalyzer exists, utilize hydrogen that reducing nitrate radical is become azanol; (b) oximation reaction district with so that formed azanol in azanol reaction district and pimelinketone carry out oximation reaction, forms cyclohexanone-oxime; (c) purifying area is in order to remove the organic pollutant in this inorganic treating liquid; And (d) adjust the district, comprise the nitric acid absorption tower that nitrate ion is provided, this nitric acid absorption tower is in order to replenish the nitrate ion content in this inorganic treating liquid, this inorganic treating liquid is divided into first part's inorganic treating liquid that enters nitric acid absorption tower and the second section inorganic treating liquid that does not enter nitric acid absorption tower after entering this adjustment district, this first part's inorganic treating liquid is no more than 20% of this inorganic treating liquid cumulative volume, and this first part's inorganic treating liquid is after entering the additional nitrate ion adjustment composition of nitric acid absorption tower, mix with this second section inorganic treating liquid again, thereby the azanol that can reduce in this inorganic treating liquid destroys the ratio of losing because of decomposition.On the other hand, the purifying area of this system can be removed the high boiling point organic pollutant in the inorganic treating liquid effectively, in order to avoid because of the employed catalyzer of murder by poisoning azanol reaction, and the selection rate of reduction activity of such catalysts and azanol reaction, more favourable manufacturing high density azanol.
Description of drawings
Fig. 1 is the synoptic diagram of known azanol-oximate circular treatment;
Fig. 2 is the simplified diagram of first specific examples of hydroxylamine-oximation circulatoing system of the present invention; And
Fig. 3 is the simplified diagram of second specific examples of hydroxylamine-oximation circulatoing system of the present invention.
[major parts nomenclature]
10 azanol reaction towers, 20 pre-mixing grooves
30 Oximation towers, 50 extraction towers
70 stripping towers, 80 activated carbon adsorption grooves
90 nitric acid absorption towers
101,103,105,107,109,111,113,115,117,119 pipelines
121,123,125,127,129,131,133,135,137,139 pipelines
Embodiment
Below use specific specific examples explanation embodiments of the present invention, those skilled in the art can understand other advantage of the present invention and effect easily by the disclosed content of this specification sheets.
" total content of organic carbon " of the present invention is that the gross weight with inorganic treating liquid is a benchmark, and all organism are in the total concn of carbon.
Fig. 2 is the synoptic diagram of first specific examples of hydroxylamine-oximation circulatoing system of the present invention.In this specific examples, this system comprises the azanol reaction district with azanol reaction tower (10); Oximation reaction district with Oximation tower (30); Comprise extraction tower (50), stripping tower (70), the purifying area that reaches activated carbon adsorption groove (80) and adjustment district with nitric acid absorption tower (90).Use phosphoric acid as the acid buffer agent in the inorganic treating liquid, the phosphoric acid salt inorganic treating liquid and the hydrogen that will contain hydrogen ion more than 2.80 moles/kilogram, the phosphoric acid salt more than 2.4 moles/kilogram, the free nitric acid more than 0.2 mole/kilogram are fed to azanol reaction tower (10) via pipeline 101,103 respectively, under the catalytic condition of noble metal catalyst, utilize hydrogen that reducing nitrate radical is become azanol, synthetic concentration is more than 1.00 moles/kilogram, and unreacted hydrogen and other gas are discharged by pipeline 105.
The inorganic treating liquid that contains the high-concentration phosphoric acid azanol imports the oximation reaction district through pipeline 107 by azanol reaction tower (10), and from Oximation tower (30) its top feed in this oximation reaction district.By this Oximation tower (30) bottom feed, oximation reaction is carried out in contact to the organic phase reaction solution that contains pimelinketone under adverse current through pipeline 113,115.This oximation reaction is preferably the temperature at 40 to 60 ℃, and carries out under the condition of normal atmosphere, subatmospheric or supercharging.After finishing oximation reaction, the organic phase that contains cyclohexanone-oxime,, is preferably more than the 35 weight % more than the about 25 weight % of the cyclohexanone-oxime concentration in this organic phase via pipeline 117 overflow dischargings from Oximation tower (30) top.Remaining phosphoric acid salt inorganic treating liquid is from Oximation tower (30) bottom discharge.
From the phosphoric acid salt inorganic treating liquid of this Oximation tower (30) bottom discharge, enter the purifying area that comprises extraction tower (50), stripping tower (70), reaches activated carbon adsorption groove (80) via pipeline 119.In extraction tower (50), use toluene as solvent, this solvent is fed to extraction tower (50) via pipeline 121 and extracts, to remove remaining cyclohexanone-oxime.Organic solvent system after the extraction sends this Oximation tower (30) back to through pipeline 123, and the phosphoric acid salt inorganic treating liquid after the extraction is then discharged from this extraction tower (50) bottom.
Send into stripping tower (70) from the inorganic treating liquid that this extraction tower (50) is discharged via pipeline 125, carry out stripping, further remove remaining organic pollutant.Wherein, the pimelinketone that the cyclohexanone-oxime hydrolysis forms and other organic substance and water are discharged this stripping tower (70) via pipeline 127, inorganic treating liquid behind the stripping is sent into activated carbon adsorption groove (80) via pipeline 129, removes high boiling point organic pollutant in this inorganic treating liquid by activated carbon adsorption.
In system of the present invention, finish in the inorganic treating liquid of purifying treatment of extraction, stripping and activated carbon adsorption, total content of organic carbon is reduced to below the 0.02 weight %, is preferably to be reduced to below the 0.015 weight %, is more preferred to be reduced to below the 0.01 weight %.
Then, finish the inorganic treating liquid of purifying treatment, send into through pipeline 131 and adjust the district.Adjust in the district in this, inorganic treating liquid is divided into the first part's inorganic treating liquid that enters the additional nitrate ion of nitric acid absorption tower (90), and through not entering the second section inorganic treating liquid of nitric acid absorption tower (90).In this specific examples, this nitric acid absorption tower (90) imports ammonia and air respectively with preparation nitric acid by 137 and 139, but not limited thereto, directly imports the preparation that nitric acid replaces nitric acid, also can reach the effect of replenishing nitrate ion.In the cumulative volume of inorganic treating liquid, the inorganic treating liquid of this first part is no more than 20 volume %, is preferably to be no more than 15 volume %.This first part's inorganic treating liquid is sent into nitric acid absorption tower through pipeline 133, after the nitrate ion adjustment that additional oximation reaction is lost is formed, mix with second section inorganic treating liquid again by pipeline 135, send into azanol reaction tower (10) through pipeline 101, as the feeding liquid of making phosphatic hydroxylamine.
Calculate by analysis, in system of the present invention, this is fed to the phosphoric acid salt inorganic treating liquid of hydroxylamine reactor (10), the content of its phosphatic hydroxylamine is in 0.02 to 0.08 mole/kilogram scope, the amount that azanol loses because of decomposition accounts for below 1.0% of azanol total amount, is preferably to account for below 0.5% of azanol total amount.On the other hand, it is more than 2.80 moles/kilogram that this phosphoric acid salt inorganic treating liquid that is fed to hydroxylamine reactor (10) meets hydrogen ion concentration, phosphate concn is more than 2.4 moles/kilogram, and free concentration of nitric acid is the standard more than 0.2 mole/kilogram, and reduce the content of organic pollutant effectively through purifying treatment after, be more suitable for being used to make the high-concentration phosphoric acid azanol, promptly make concentration more than 1.00 moles/kilogram, be preferably concentration more than 1.15 moles/kilogram, be more preferred from concentration more than 1.3 moles/kilogram, be more preferred from the phosphatic hydroxylamine of concentration more than 1.5 moles/kilogram again.
Fig. 3 is the synoptic diagram of the present invention's second specific examples, and same parts is represented with same-sign.In this specific examples, this system includes the have hydroxylamine reactor azanol reaction district of (10); Pre-mixing groove (20); Oximation reaction district with Oximation tower (30); Comprise extraction tower (50), stripping tower (70), the purifying area that reaches activated carbon adsorption groove (80) and adjustment district with nitric acid absorption tower (90).The phosphoric acid salt inorganic treating liquid and the hydrogen that contain hydrogen ion more than 2.80 moles/kilogram, the phosphoric acid more than 2.4 moles/kilogram, the free nitric acid more than 0.2 mole/kilogram are fed to hydroxylamine reactor (10) via pipeline 101,103 respectively, under the catalytic condition of noble metal catalyst, utilize hydrogen that reducing nitrate radical is become azanol, synthetic concentration is higher than the high-concentration phosphoric acid azanol more than 1.00 moles/kilogram, and unreacted hydrogen and other gas are discharged by pipeline 105.
The inorganic treating liquid that contains the high-concentration phosphoric acid azanol is sent into pre-mixing groove (20) through pipeline 107,109 respectively in the same way with the organic phase reaction solution that contains pimelinketone, carries out pre-mixing under 30 to 50 ℃ temperature condition, forms mixed reaction solution.In premixed mixed reaction solution, the concentration of this phosphatic hydroxylamine has been reduced to below 80% of original content, is preferably below 75%, is more preferred from below 65%, is more preferred from again below 55%, especially is more preferred from below 50%, to improve the efficient of follow-up oximation reaction.The organic phase reaction solution that contains pimelinketone comprises pimelinketone and organic solvent, and the example of this organic solvent comprises, but non-benzene,toluene,xylene, methylcyclopentane, hexanaphthene and composition thereof etc. of being limited to.
Enter the oximation reaction district through premixed mixed reaction solution through pipeline 111, and from Oximation tower (30) its top feed in this oximation reaction district, by this Oximation tower (30) bottom feed, oximation reaction is carried out in contact to the organic phase reaction solution that contains pimelinketone under adverse current through pipeline 113,115.The preferable temperature at 40 to 60 ℃ of this oximation reaction, and carry out under the condition of normal atmosphere, subatmospheric or supercharging.After finishing oximation reaction, via pipeline 117 overflow dischargings, the cyclohexanone-oxime concentration of this organic phase is more than the 30 weight % to the organic phase that contains cyclohexanone-oxime, is preferably more than the 35 weight %, is more preferred from again more than the 40 weight % from Oximation tower (30) top.Remaining phosphoric acid salt inorganic treating liquid is from Oximation tower (30) bottom discharge.
From the phosphoric acid salt inorganic treating liquid of this Oximation tower (30) bottom discharge, enter the purifying area that comprises extraction tower (50), stripping tower (70), reaches activated carbon adsorption groove (80) via pipeline 119.In extraction tower (50), use toluene as solvent, this solvent is fed to extraction tower (50) via pipeline 121 and extracts, to remove remaining cyclohexanone-oxime.Organic solvent after the extraction is sent this Oximation tower (30) back to through pipeline 123, and the phosphoric acid salt inorganic treating liquid after the extraction is then discharged from this extraction tower (50) bottom.
Send into stripping tower (70) from the inorganic treating liquid that this extraction tower (50) is discharged via pipeline 125, further remove remaining organic pollutant.The pimelinketone that the cyclohexanone-oxime hydrolysis forms and other organic substance and water are discharged this stripping tower (70) via pipeline 127, inorganic treating liquid behind the stripping is sent into activated carbon adsorption groove (80) via pipeline 129, removes high boiling point organic pollutant in this inorganic treating liquid by activated carbon adsorption.
In this specific examples, to finish in the inorganic treating liquid of purifying treatment of extraction, stripping and activated carbon adsorption, total content of organic carbon is reduced to below the 0.02 weight %, is preferably to be reduced to below the 0.015 weight %, is more preferred to be reduced to below the 0.01 weight %.
Then, finish the inorganic treating liquid of purifying treatment, send into through pipeline 131 and adjust the district.Adjust in the district at this, inorganic treating liquid is divided into the first part's inorganic treating liquid that enters the additional nitrate ion of nitric acid absorption tower (90), and through not entering the second section inorganic treating liquid of nitric acid absorption tower (90).In the cumulative volume of inorganic treating liquid, the inorganic treating liquid of this first part is no more than 20 volume %, is preferably to be no more than 15 volume %.The inorganic treating liquid of this first part is sent into nitric acid absorption tower through pipeline 133, after the nitrate ion adjustment that additional oximation reaction is lost is formed, mix with second section inorganic treating liquid again, send into hydroxylamine reactor (10) as the feeding liquid of making phosphatic hydroxylamine through pipeline 101 by pipeline 135.
Calculate by analysis, in system of the present invention, this is fed in the phosphoric acid salt inorganic treating liquid of azanol reaction tower (10), the content of phosphatic hydroxylamine is in 0.02 to 0.08 mole/kilogram scope, the amount that azanol loses because of decomposition is about below 1.0% of azanol total amount, is preferably below 0.50% of azanol total amount.On the other hand, this phosphoric acid salt inorganic treating liquid that is fed to hydroxylamine reactor (10) meets that hydrogen ion concentration is more than 2.80 moles/kilogram, phosphoric acid concentration is more than 2.4 moles/kilogram and free concentration of nitric acid is a standard more than 0.2 mole/kilogram, be suitable for making the high-concentration phosphoric acid azanol, promptly make concentration more than 1.00 moles/kilogram, be preferably concentration more than 1.15 moles/kilogram, be more preferred from concentration more than 1.3 moles/kilogram, be more preferred from the phosphatic hydroxylamine of concentration more than 1.5 moles/kilogram again.
Hydroxylamine-oximation circulatoing system of the present invention is with the aqueous reaction medium of phosphoric acid salt inorganic treating liquid as full cycle, in hydroxylamine reactor, utilize the hydrogen reducing nitrate ion to form phosphatic hydroxylamine, enter oximation reaction device and pimelinketone again and carry out oximation reaction, make cyclohexanone-oxime.In the system of the present invention, can more effectively remove organic pollutant through purifying step such as extraction, stripping, activated carbon adsorption.And in this system, inorganic treating liquid only part enters the additional nitrate ion of nitric acid absorption tower, mix with remaining inorganic treating liquid again after adjusting composition, loop back the azanol reaction district, as the feeding liquid of making phosphatic hydroxylamine, the azanol that can reduce in this inorganic treating liquid destroys the ratio of losing because of decomposition.
Embodiment
Embodiment 1
Time per unit is fed to hydroxylamine reactor with the phosphoric acid salt inorganic treating liquid continuously, contains 2.88 moles/kilogram hydrogen ion, 2.68 moles/kilogram phosphoric acid salt, 0.20 mole/kilogram free nitric acid in this inorganic treating liquid.Under the hydrogen partial pressure condition of 53 ℃ temperature and 55%, use palladium/activated carbon catalyst of 10% (Japanese degussa company produce) to carry out catalysis, synthetic phosphatic hydroxylamine.In the phosphoric acid salt inorganic treating liquid of this hydroxylamine reactor outlet, institute's synthetic phosphatic hydroxylamine concentration is 1.14 moles/kilogram.
This phosphatic hydroxylamine inorganic treating liquid carries out oximation reaction (the Oximation tower service temperature is 51 ℃) by Oximation tower top and bottom feed to Oximation tower respectively continuously with the toluene solution that contains pimelinketone, and azanol is 0.90 to the mol ratio of pimelinketone.Time per unit is from the organic phase of this Oximation tower top overflow discharging, and cyclohexanone-oxime concentration is 33.1 weight %, and the phosphoric acid salt inorganic treating liquid that discharge the Oximation tower bottom extracts in extraction tower.
Use toluene to make solvent, under 70 ℃ temperature condition, in extraction tower, extract.Inorganic treating liquid through extraction is discharged by the extraction tower bottom.Then, under 130 ℃ temperature condition, carry out stripping, remove the organic pollutant in this inorganic treating liquid, contain 0.045 mole/kilogram phosphatic hydroxylamine, total content of organic carbon 0.0216 weight % through steam stripped inorganic treating liquid.
Inorganic treating liquid behind the stripping is sent into the activated carbon adsorption tower, under 20 ℃ temperature condition, carry out activated carbon adsorption,, finish the purification of inorganic treating liquid to remove high boiling organic impurity.Contain 0.045 mole/kilogram phosphatic hydroxylamine in the inorganic treating liquid after the purification, total content of organic carbon is 0.0089 weight %.
After this inorganic treating liquid through purifying enters and adjusts the district, in the cumulative volume of this inorganic treating liquid, the inorganic treating liquid of 12 volume % enters nitric acid absorption tower and replenishes nitrate ion, then mixes with remaining inorganic treating liquid again, be fed to the azanol reaction district, as the feeding liquid of making phosphatic hydroxylamine.Analyze the phosphatic hydroxylamine concentration of this feeding liquid, only 0.005 mole/kilogram azanol decomposed and destroys, so in this hydroxylamine-oximation circulatoing system, in the total amount of azanol, the ratio that this azanol decomposes loss is 0.47%.
Embodiment 2
Time per unit is fed to hydroxylamine reactor with the phosphoric acid salt inorganic treating liquid continuously, contains 3.45 moles/kilogram hydrogen ion, 3.05 moles/kilogram phosphoric acid salt, 0.58 mole/kilogram free nitric acid in this inorganic treating liquid.Under the hydrogen partial pressure condition of 53 ℃ temperature and 55%, use palladium/activated carbon catalyst of 10% (Japanese degussa company produce) to carry out catalysis, synthetic phosphatic hydroxylamine.In the phosphoric acid salt inorganic treating liquid of this hydroxylamine reactor outlet, institute's synthetic phosphatic hydroxylamine concentration is 1.41 moles/kilogram.
The inorganic treating liquid elder generation of this phosphatic hydroxylamine is fed to the premixing reaction device in the same way with the toluene solution of part pimelinketone, carries out pre-mixing under temperature of 37 ℃ and an atmospheric pressure condition.In the mixed reaction solution of this premixing reaction device discharging, the phosphatic hydroxylamine concentration ratio is reduced to 0.45 of original content.
From the Oximation tower its top feed, the toluene solution of another part pimelinketone is from the Oximation tower bottom feed through premixed mixed reaction solution, and counter current contact is carried out oximation reaction under 51 ℃ temperature condition, and azanol is 0.90 to the mol ratio of pimelinketone (two portions total amount).Time per unit is from the organic phase of this Oximation tower top overflow discharging, and cyclohexanone-oxime concentration is 38.4 weight %.
Use toluene to make solvent, under 70 ℃ temperature condition, in extraction tower, extract.Inorganic treating liquid through extraction is discharged by the extraction tower bottom.Then, carry out stripping under 130 ℃ temperature condition, remove the organic pollutant in this inorganic treating liquid, contain 0.062 mole/kilogram phosphatic hydroxylamine in steam stripped inorganic treating liquid, total content of organic carbon is 0.0248 weight %.
Inorganic treating liquid behind the stripping is sent into the activated carbon adsorption tower, under 20 ℃ temperature condition, carry out activated carbon adsorption,, finish the purification of inorganic treating liquid to remove high boiling organic impurity.Contain 0.062 mole/kilogram phosphatic hydroxylamine in the inorganic treating liquid after the purification, total content of organic carbon is 0.0113 weight %.
After this inorganic treating liquid through purifying enters and adjusts the district, cumulative volume in this inorganic treating liquid, the inorganic treating liquid system of 14 volume % enters nitric acid absorption tower and replenishes nitrate ion, then mix with remaining inorganic treating liquid again, be fed to the azanol reaction district, as the feeding liquid of making phosphatic hydroxylamine.Analyze the phosphatic hydroxylamine concentration of this feeding liquid, only 0.009 mole/kilogram azanol decomposed and destroys, so in this hydroxylamine-oximation circulatoing system, in the total amount of azanol, the ratio that this azanol decomposes loss is 0.63%.
Embodiment 3
Time per unit is fed to hydroxylamine reactor with the phosphoric acid salt inorganic treating liquid continuously, contains 4.00 moles/kilogram hydrogen ion, 3.27 moles/kilogram phosphoric acid salt, 0.72 mole/kilogram free nitric acid in this inorganic treating liquid.Under the hydrogen partial pressure condition of 53 ℃ temperature and 55%, use palladium/activated carbon catalyst of 10% (Japanese degussa company produce) to carry out catalysis, synthetic phosphatic hydroxylamine.In the phosphoric acid salt inorganic treating liquid of this hydroxylamine reactor outlet, institute's synthetic phosphatic hydroxylamine concentration is 1.64 moles/kilogram.
The inorganic treating liquid elder generation of this phosphatic hydroxylamine is fed to the premixing reaction device in the same way with the toluene solution of part pimelinketone, carries out pre-mixing under temperature of 37 ℃ and an atmospheric pressure condition.In the mixed reaction solution of this premixing reaction device discharging, the phosphatic hydroxylamine concentration ratio is reduced to 0.63 of original content.
From the Oximation tower its top feed, the toluene solution of another part pimelinketone is from the Oximation tower bottom feed through premixed mixed reaction solution, and counter current contact is carried out oximation reaction under 51 ℃ temperature condition, and azanol is 0.90 to the mol ratio of pimelinketone (two portions total amount).Time per unit is from the organic phase of this Oximation tower top overflow discharging, and cyclohexanone-oxime concentration is 42.2 weight %.
Use toluene to make solvent, under 70 ℃ temperature condition, in extraction tower, extract.Inorganic treating liquid through extraction is discharged by the extraction tower bottom.Then, carry out stripping under 130 ℃ temperature condition, remove the organic pollutant in this inorganic treating liquid, contain 0.080 mole/kilogram phosphatic hydroxylamine in steam stripped inorganic treating liquid, total content of organic carbon is 0.0287 weight %.
Inorganic treating liquid behind the stripping is sent into the activated carbon adsorption tower, under 20 ℃ temperature condition, carry out activated carbon adsorption,, finish the purification of inorganic treating liquid to remove the high boiling point organic impurity.Contain 0.080 mole/kilogram phosphatic hydroxylamine in the inorganic treating liquid after the purification, total content of organic carbon is 0.0139 weight %.
After this inorganic treating liquid through purifying enters and adjusts the district, in the cumulative volume of this inorganic treating liquid, the inorganic treating liquid of 17 volume % enters nitric acid absorption tower and replenishes nitrate ion, then mixes with remaining inorganic treating liquid again, be fed to the azanol reaction district, as the feeding liquid of making phosphatic hydroxylamine.Analyze the phosphatic hydroxylamine concentration of this feeding liquid, only 0.014 mole/kilogram azanol decomposed and destroys, so in this hydroxylamine-oximation circulatoing system, in the total amount of azanol, the ratio that this azanol decomposes loss is 0.85%.
The foregoing description only is illustrative principle of the present invention and effect thereof, but not is used to limit the present invention.Those skilled in the art all can be under spirit of the present invention and category, and the foregoing description is modified and changed.Therefore, the scope of the present invention, claims are described as described later.
Claims (10)
1. hydroxylamine-oximation circulatoing system comprises:
(a) azanol reaction district in order in containing the inorganic treating liquid of acid buffer agent, under the condition that catalyzer exists, utilizes hydrogen that reducing nitrate radical is become azanol;
(b) oximation reaction district with so that formed azanol in azanol reaction district and pimelinketone carry out oximation reaction, forms cyclohexanone-oxime;
(c) purifying area is in order to remove the organic pollutant in this inorganic treating liquid; And
(d) adjust the district, comprise the nitric acid absorption tower that nitrate ion is provided, this nitric acid absorption tower is in order to replenish the nitrate ion content in this inorganic treating liquid, this inorganic treating liquid is divided into first part's inorganic treating liquid that enters nitric acid absorption tower and the second section inorganic treating liquid that does not enter nitric acid absorption tower after entering this adjustment district, this first part's inorganic treating liquid is no more than 20% of this inorganic treating liquid cumulative volume, and this first part's inorganic treating liquid is after entering the additional nitrate ion of nitric acid absorption tower, mix with this second section inorganic treating liquid again, wherein, this purifying area is provided with the activated carbon adsorption groove.
2. the system as claimed in claim 1 is characterized in that, contains azanol and organic pollutant in this inorganic treating liquid.
3. system as claimed in claim 2 is characterized in that this organic pollutant comprises ketone compounds, oxime compound, carboxylic acid compound and aminated compounds.
4. the system as claimed in claim 1 is characterized in that, this purifying area also comprises extraction tower.
5. the system as claimed in claim 1 is characterized in that, this purifying area also comprises stripping tower.
6. system as claimed in claim 5 is characterized in that, this stripping tower carries out stripping under 50 to 150 ℃ condition.
7. the system as claimed in claim 1 is characterized in that, this acid buffer agent is a phosphoric acid salt.
8. system as claimed in claim 7 is characterized in that, this azanol reaction district institute synthetic synthetics is that concentration is higher than 1.0 moles/kilogram phosphatic hydroxylamine.
9. system as claimed in claim 8 is characterized in that, also comprises the pre-mixing groove between this azanol reaction district and this oximation reaction district.
10. system as claimed in claim 9 is characterized in that, this pimelinketone carries out the non-reverse pre-mixing that contacts with this inorganic treating liquid that contains the high-concentration phosphoric acid azanol, makes the concentration ratio of this phosphatic hydroxylamine be reduced to below 80% of original content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100006864A CN100545083C (en) | 2007-01-16 | 2007-01-16 | A kind of hydroxylamine-oximation circulatoing system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100006864A CN100545083C (en) | 2007-01-16 | 2007-01-16 | A kind of hydroxylamine-oximation circulatoing system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101224880A CN101224880A (en) | 2008-07-23 |
| CN100545083C true CN100545083C (en) | 2009-09-30 |
Family
ID=39857122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100006864A Active CN100545083C (en) | 2007-01-16 | 2007-01-16 | A kind of hydroxylamine-oximation circulatoing system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100545083C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483221A (en) * | 2012-06-12 | 2014-01-01 | 刘建青 | Preparation method of cyclohexanone oxime |
| CN102775326B (en) * | 2012-08-07 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of method reducing inactivation of hydroxylamine inorganic liquid |
| CN104262196B (en) * | 2014-09-02 | 2016-07-27 | 河北美邦工程科技有限公司 | A kind of Ammoximation reaction and separation coupling technique and device |
| CN105731401B (en) * | 2016-03-25 | 2018-01-30 | 巨化集团技术中心 | A kind of method for producing hydroxylamine hydrochloride |
| CN108017556A (en) * | 2016-11-04 | 2018-05-11 | 深圳市志邦科技有限公司 | A kind of new synthetic method of isocyanates crosslinking agent sealer |
| CN109836353A (en) * | 2017-11-27 | 2019-06-04 | 黄飞熊 | The method of optimization manufacture cyclohexanone oxime |
| WO2020078898A1 (en) * | 2018-10-17 | 2020-04-23 | Cap Iii B.V. | An improved process for the production of oximes |
-
2007
- 2007-01-16 CN CNB2007100006864A patent/CN100545083C/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101224880A (en) | 2008-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100545083C (en) | A kind of hydroxylamine-oximation circulatoing system | |
| JP3361200B2 (en) | Exhaust gas treatment method and equipment for electron beam irradiation | |
| US7732640B2 (en) | Process for urea production from ammonia and carbon dioxide | |
| CN103496777B (en) | Pretreatment method of ammonia-nitrogen wastewater | |
| EP2114872B1 (en) | Process and plant for the production of an aqueous solution comprising urea | |
| CN104785102A (en) | Energy-saving and efficient N2O and NOx removing process | |
| CN105396460B (en) | High-efficiency combined removal of N2O and NOxMethod (2) | |
| CN101927126B (en) | Method for carrying out uncatalyzed direct oxidation treatment on gas containing nitric oxide by using Venturi oxidizer | |
| CN102452737A (en) | Ammonium sulfate wastewater treatment method during acrylonitrile production process | |
| EP1299353B1 (en) | Process for the preparation of cyclohexanone oxime | |
| CN206375773U (en) | A kind of high ammonia-nitrogen sewage treatment system | |
| KR100843925B1 (en) | Process for the production of cyclohexanone oxime | |
| US7785549B2 (en) | Recycling system for hydroxylamine formation and oximation | |
| US5364609A (en) | Process for the preparation and processing of a hydroxylammonium salt solution | |
| CN105819564B (en) | A kind of processing method of paraformaldehyde waste water | |
| US20040039231A1 (en) | Process for the production of cyclohexanone oxime | |
| TWI813796B (en) | An improved process for the production of oximes | |
| CN100500641C (en) | Method for manufacturing hydroxylamine | |
| CN105536500A (en) | Method for removing nitrogen oxide in airflow | |
| CN114380708A (en) | Method for recovering catalyst for synthesizing hydrazine hydrate intermediate | |
| CN113289472A (en) | Method for denitration of flue gas by using ozone | |
| US7381843B2 (en) | Method for preparing hydroxylamine | |
| CN117945367A (en) | Method for removing ammonium nitrate from nitric acid solution | |
| CN114618270A (en) | Containing NOxTail gas normal-temperature denitration device and method | |
| CN101531380A (en) | Ammonia reclaiming technology in process of preparing m-dicyanobenzene by using ammonia oxidation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |