CN103492312A - Method for preparing hydroxylamine - Google Patents
Method for preparing hydroxylamine Download PDFInfo
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- CN103492312A CN103492312A CN201280019822.3A CN201280019822A CN103492312A CN 103492312 A CN103492312 A CN 103492312A CN 201280019822 A CN201280019822 A CN 201280019822A CN 103492312 A CN103492312 A CN 103492312A
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- nitrate
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- azanol
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
- C01B21/1409—Preparation
- C01B21/1418—Preparation by catalytic reduction of nitrogen oxides or nitrates with hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D225/00—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom
- C07D225/02—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom not condensed with other rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention relates to a method for preparing hydroxylamine in a continuous process, comprising feeding nitrate and phosphate in an acidic aqueous liquid into a reaction zone and reducing nitrate with hydrogen thereby forming hydroxylamine, wherein the nitrate concentration in the reaction zone is less than 1.0 mol/kg, as determined in the liquid leaving the reaction zone, wherein the molar ratio of nitrate to phosphate in the reaction zone is 0.5 or less, and wherein the molar ratio of ammonia to nitrate is in the range of from 2.2 to 7; a method for preparing an oxime and a method of preparing a lactam comprising said method for preparing hydroxylamine.
Description
The present invention relates to prepare the method for azanol in successive processes, also relate to the method for preparing oxime and the method for preparing lactan.
Azanol (following also referred to as " HYAM ") is the common agents in countless organic reactions and inorganic reaction.It is particularly suitable for oxime, particularly in the preparation of cyclohexanone-oxime, wherein oxime, hexanolactam be reset and be converted to cyclohexanone-oxime can through Beckmann subsequently particularly.The Beckmann rearrangement process that is used for preparing hexanolactam is known in the art, such as at Ullmann ' s Encyclopedia of Industrial Chemistry, as the 7th edition (2005), Chapter on Caprolactam is (in DOI:10.1002/14356007.a05.031 (retrieval on February 18th, 2011).Described other oximes that use azanol to prepare, they comprise cyclododecanone oxime (as EP-A1329448) and Diacetylmonoxime.
The method for preparing azanol is also as known in the art.And, delivered the patent of many pieces of writing about this theme.For example GB-A-1287303 and US-5364609 relate in phosphate buffer solution with molecular hydrogen and reduce the method for nitrate.
DSM's
cyclohexanone-oxime technique (referring to for example H.J.Damme, J.T.van Goolen and A.H.de Rooij, Cyclohexanone oxime made without by-product (NH
4)
28O
4, on July 10th, 1972, the 54/55th page of Chemical Engineering, or Ullmann ' s encyclopedia of industrial chemistry (2005), under the Chapter Caprolactam, the 6/7th page; DOI:10.1002/14356007.a05.031 (retrieval on February 18th, 2011)) utilized the liquid (inorganic liquid and organic liquid) of two kinds of recycles, carried out a plurality of reactions and operation in these liquid.Inorganic liquid, comprise the aqueous solution of phosphoric acid and ammonium nitrate, is fed in hydrogenation reactor, in this reactor, produces azanol.Through with the hydrogen reduction nitrate ion, forming azanol, this process is by heterogeneous catalyst (carbon is as the palladium-containing catalyst of carrier) catalysis.
In the gas-liquid reaction device, gaseous hydrogen contacts with the inorganic liquid containing nitrate ion of circulation, also with buffering acid, with catalyzer, contacts.Hydrogeneous gas phase circulates by recycle compressor in whole bubbling column reactor.Fresh hydrogen is fed in recycle gas, discharges to keep constant hydrogen pressure from system on a small quantity.The gaseous by-product N that removes the inertia gaseous component in fresh hydrogen and generate by gas purging
2and N
2o.
By ultra-large type (Mammoth) pump principle, make solution-air suspension from inflation reactor (gassed reactor) partly, through gas-liquid separator circulation, arrive the filter post (filter candles) filtration fraction, and remove the heat of reaction via heat exchanger, then get back to inflation reactor part.
Then, the inorganic liquid obtained after filtering is contacted to the mixture that this organic liquid is toluene and pimelinketone with organic liquid in the oximate part.Herein, pimelinketone almost changes into cyclohexanone-oxime quantitatively.The organic phase containing cyclohexanone-oxime that distillation obtains reclaims toluene.
Thoroughly purifying leaves the inorganic liquid of oximate part, protects the catalyzer of hydroxylamine reactor.This can be by with the realization of getting off: the toluene extraction, then use steam stripped.In stripping tower, also removed and prepared the water that azanol forms together with when cyclohexanone-oxime.A small amount of ammonia by product is still stayed in solution, but by for NO and N0
2gaseous mixture (for example nitrogen protoxide and nitrogen peroxide; Below also be called nitrous gases) resorber in ammonia is changed into to nitrogen, prevent from gathering.
Finally, the consumption of nitrate deserves redress.Therefore, required nitrous gases generates in the ammonia fuel element.
EP1947056A1 has described the method for preparing azanol, and it is by realizing with hydrogen reducing nitrate containing in the inorganic treatment soln of acid buffer agent under the existence of catalyzer, and this is as the azanol combined and the part of oximate system.This patent has instructed this recirculation system can reduce the rate of loss of azanol in inorganic treatment soln, and reduces organic impurity.
US2006/0079678A1 has described the method for preparing hydroxylammonium, and it is by realizing with hydrogen catalysis reduction nitrate or oxynitride, and this is as the part of the system of producing cyclohexanone-oxime.This patent has been instructed and has been distilled with improvement hexamethylene ketoamine product stream, comprises that the pimelinketone distilled out from it is to the synthetic regional circulation of cyclohexanone-oxime.
By people, decades have been known although prepare azanol by nitrate, and the mode of improving known preparation method is thoroughly studied in these years, but current known industrial technology, continuous processing normally, still there are all drawbacks, especially when in existing factory or while attempting to increase throughput in the new factory based on Known designs.
A kind of mode that (under fixing azanol concentration) increases productivity in reactor is for example to reduce liquid residence time, in conjunction with the catalyst concn and/or the temperature of raising and/or the hydrogen dividing potential drop of raising that increase.Some the time, in the situation that do not need with high investmently in other parts to circulation, can not improve again the liquid feeding rate.
For example, described in EP-1303480-B1 and US-6759556, a kind of mode of further boosting productivity is by improving azanol concentration.By improving azanol concentration, azanol and the more effective azanol conversion of acquisition during pimelinketone react in the oximation reaction step of downstream.Same by improve phosphate concn (with > phosphoric acid of 2mol/mol/azanol ratio), the carbonyl compound (it plays the effect of catalyzer poison) entered in inorganic cycle for the treatment of is less, this is conducive to high reactivity and the selectivity of hydrogenation catalyst.
Yet the contriver recognizes that it is problematic improving azanol concentration.For example, special investigating period in traditional factory, the present inventor finds that the feeding rate improve reagent in order to improve the azanol productivity can cause scale problems, the problem caused due to the crystallization of crystallization, especially biphosphate ammonium salt ((mono) ammonium hydrogen phosphate salts) particularly.This fouling meeting causes for example strainer or cooling tube, the conversion zone downstream, obstruction.Particularly, the contriver finds, by improve the azanol production concentration and process condition is remained on the value that is conducive to the process described in EP-1303480-B1 and US-6759556 simultaneously, is present in Tc in the treatment liq in inorganic cycle for the treatment of and raises.
If the temperature of reaction mixture is brought down below its Tc, crystal formation.When if this reactor surface in cooling generation occurs, crystal can make reaction and cooling isolation, and the loss of meeting generating process control.This can easily accelerate serious scale and need the stopped reaction device to clean by root, and this is serious interruption.For fear of fouling and technology trouble, the Tc of reaction mixture preferably remains on than the higher temperature of temperature of the water coolant of the heat that is used for removing hydrogenation.This has limited the exercisable maximum azanol production concentration of nitrate hydrogenation reactor.
An object of the present invention is to provide a kind of method for preparing the novelty of azanol in successive processes, it can be used as the alternative method of currently known methods, provides particularly and compares with the traditional method operated in identical production unit and can under the azanol throughput improved, operation avoid the method for salt as the novelty of the crystallization of ammonium hydrogen phosphate salt simultaneously.
Another purpose is to provide the method for preparing azanol, and one ton of azanol of the every preparation of the method needs less catalyzer.
Obviously found out one or more other purposes that can realize by the present invention by following description.
Now be surprised to find one or more can the realization by the following in these purposes: form therein in the conversion zone of azanol with specific nitrate concentration, specific nitrate and phosphoric acid salt ratio and specifically ammonia and nitrate ratio are carried out the preparation of azanol.
Therefore, the present invention relates to a kind of method for preparing azanol in successive processes, it comprises the nitrate in acidic aqueous liquid and phosphoric acid salt is fed to conversion zone and uses hydrogen reduction nitrate, thereby formation azanol, wherein control nitrate and phosphoric acid salt, hydrogen and temperature, so that in conversion zone, the concentration of nitrate is less than 1.0mol/kg, the concentration of nitrate records in leaving the liquid of conversion zone; In conversion zone, nitrate and phosphatic mol ratio are 0.5 or less; And the mol ratio of ammonia and nitrate is in 2.2 to 7 scope.The reduction of nitrate is the reaction of catalysis normally.
Have been found that according to the present invention, the preparation process of azanol can be strengthened, thereby improves throughput.Surprisingly, at relatively low nitrate concentration, with under relative low nitrate and phosphoric acid salt ratio, it is feasible improving throughput.After all, the nitrate hydrogenation is considered to the behavior according to Langmuir-Hinshelwood kinetics type, and wherein in known raising conversion zone, the concentration of nitrate can improve speed of reaction.Thus, those of ordinary skills can expect and be, the concentration that reduces nitrate can reduce nitrate reduction speed, thereby reduce azanol throughput.
In conversion zone, the concentration of nitrate is less than 1.0mol/kg, in leaving the liquid of conversion zone, records; Nitrate and phosphatic mol ratio 0.5 or less in conversion zone; And the mol ratio of ammonia and nitrate is in 2.2 to 7 scopes, these special parameters cause reaction mixture to have low especially Tc, but keep generating the high conversion of azanol simultaneously.
Therefore, the present invention provides a kind of mode for preparing azanol that simultaneously has the risk of the fouling that the crystallization due to material in conversion zone of reduction causes with favourable throughput astoundingly.
Expection particularly: according to the present invention can be in reaction liquid (leaving conversion zone) with 1.2mol/kg or more, preferably 1.3 or more, more preferably 1.4 or more or 1.5 or more concentration obtain azanol.This high azanol concentration is favourable, because reaction system is therefore strengthened and productivity is improved.One preferred embodiment in, azanol concentration is 2mol/ (kg liquid reacting product) or less, 1.9mol/ (kg liquid reacting product) or less, 1.8mol/ (kg liquid reacting product) or less more specifically particularly.Yet, consider the risk of expected crystallization and fouling, it not is apparent in the nitrate reduction reactor, with the azanol concentration improved, operating.
In addition, the favourable part of the method according to this invention is, in order to realize specific throughput, a certain amount of azanol of every production needs less catalyzer.
Also find, with respect to azanol further application in the preparation of oxime such as cyclohexanone-oxime, the method according to this invention is favourable.Azanol leaves conversion zone with the form of product reaction mixture usually, and it normally comprises the waterborne liquid of azanol, phosphoric acid salt, any unreacted nitrate and ammonia.Mixture of reaction products prepared from azanol by discovery especially is suitable as the charging for the preparation of the method for oxime, and its advantage is by this oximation reaction product mixtures oximation reaction and/or oxime extraction more effective.
While using herein, unless otherwise specified outside, the term "or" refer to " and/or ".
While using herein, unless otherwise specified outside, term " a kind of " (a or an) refers to " at least one ".
Unless otherwise specified, for example, when mentioning ' noun ' (compound, additive) with singulative, also comprise its plural connotation.
The preparation of azanol can be suitably carried out in known being used for prepares the flow reactor of azanol.In one embodiment, reaction is carried out in the reactor that well-mixed gas/liquid system is provided.This system is known in the art, and comprises stirred-tank reactor, common loop reactor, external loop reactor and bubbling column reactor.One preferred embodiment in, use bubbling column reactor.Particularly, use the bubbling column reactor with outside gas lift (gas-lift), obtained good result.
In conversion zone, the derivative parameter (for example concentration ratio of material) of the concentration of material or concentration can be determined by following: location parameter in the sample that picks up from the treatment liq of leaving conversion zone.
As implied above, according to the present invention, in conversion zone, the concentration of nitrate is less than 1.0mg/kg, and it records in leaving the liquid of conversion zone.One preferred embodiment in, the concentration of nitrate is 0.9mol/kg or less, 0.8mol/kg or less particularly.Adopt approximately 0.70 or the concentration of less nitrate obtained particularly preferred result.In general, the concentration of nitrate is 0.3mol/kg at least, 0.4mol/kg at least particularly.Preferably, nitrate concentration is 0.45mol/kg at least, 0.50mol/kg at least more preferably.
The mol ratio of ammonia and nitrate is in 2.2 to 7 scope.For high productive rate, 6 or less, particularly 5 or less mol ratio be particularly preferred.Specifically consider, with respect to the also original azanol that forms of catalysis nitrate, this is conducive to the high catalytic activity of catalyzer.2.3 or more greatly, particularly 2.4 or larger or 25 or the mol ratio of larger ammonia and nitrate be particularly advantageous in and hang down fouling tendency.Specifically consider, with respect to the also original azanol that forms of catalysis nitrate, the mol ratio in 2.3 to 6, more preferably 2.4 to 5, most preferably 2.5 to 5 scopes is conducive to the high catalytic activity of catalyzer.
Phosphoric acid salt provides with phosphoric acid or hydrophosphate (its pH that can regulate phosphoric acid solution as oxyhydroxide or ammonia by the alkali with suitable forms) form usually.Nitrate and phosphatic mol ratio are generally at least 0.05, preferably at least 0.10.At this ratio at least 0.15, have more while carrying ground at least 0.20, obtained excellent result.Nitrate and phosphatic mol ratio be preferably 0.40 or still less, specifically low 0.35 or still less, more specifically 0.30 or still less.
Can be in a manner known way and concentration (hydrogen pressure) hydrogen is fed in conversion zone.Preferably, pressure be at least about 0.5MPa, more preferably at least about 1.0MPa.In general, hydrogen pressure is 10MPa or less.
In a favourable embodiment, be chosen in the buffering ratio in specified range.Buffering is than being defined as herein:
([H
+]+[HYAM])/[phosphoric acid salt]
Wherein:
[H
+]=H in leaving the waterborne liquid of conversion zone
+volumetric molar concentration, in mol/kg,
[HYAM]=concentration of azanol in leaving the waterborne liquid of conversion zone, in mol/kg,
[phosphoric acid salt]=in leaving the waterborne liquid of conversion zone, phosphoric acid salt (comprises with H
3pO
4, monohydric phosphate and dihydrogen phosphate the phosphoric acid salt of form) total concn, in mol/kg,
[H
+], [HYAM] and [phosphoric acid salt] concentration all the equilibrium titration by a sample as the mensuration of getting off: thereby obtain [the H of the first trim point (under about 4.2 pH) from the liquid sample of conversion zone with the NaOH aqueous solution titration of 0.25N under 25 ℃
+] concentration (" free acid "); Then to the acetone that adds molar excess in this sample, azanol is changed into to oxime and H
+, and continuing equilibrium titration, thereby reach subsequently three further isocenters, first correspondence is from the free acid of azanol (and therefore sampling in [HYAM] value); Second value that [phosphoric acid salt] is provided, last provides the value of ammonia.But, the value that does not need back herein.
Especially for the simultaneously relatively high throughput of low crystallization risk, buffering than preferably in 0.4 to 0.8 scope, particularly in 0.45 to 0.70 scope, more specifically in 0.50 to 0.65mol/mol scope.
H in reaction
+volumetric molar concentration usually in 0.4 to 0.8mol/kg scope, particularly in 0.45 to 0.70mol/kg scope, more specifically in 0.50 to 0.65mol/kg scope.
Generally with metal catalyst, carry out catalysis according to the preparation of azanol of the present invention.Suitable catalyzer is known in the art.Specifically, can use the catalyzer containing palladium.Catalyzer can comprise one or more (catalysis) metals, palladium particularly.Catalyzer is provided on carrier usually.Specifically, adopt the palladium-containing catalyst on carbon, realized good result.Usually, the catalyzer provided has the promotor for this catalyzer, for example germanium oxide.As required, can the random time in preparing the method for azanol add promotor.
Other conditions that prepare azanol itself are known in the art.Particularly, temperature can be in the scope of 20 to 70 ℃, preferably in the scope of 30 to 60 ℃, particularly in the scope of 35 to 55 ℃.
In the mixture of reaction products that prepared azanol can obtain by routine techniques from conversion zone according to the present invention, reclaim, perhaps this mixture of reaction products can be fed in further process, for example be fed to (optionally after it is processed, for example, after removing one or more components of not expecting) in the method for preparing oxime.
Therefore, the invention still further relates to the azanol that obtains in the method according to this invention purposes for the preparation of oxime.
The cause azanol prepares oxime in a manner known way.The method comprises azanol and the alkane reactive ketone will obtained in the method according to this invention usually.Alkane ketone can be ring-type or acyclic.Preferred naphthenone is pimelinketone, thereby obtains cyclohexanone-oxime; Cyclododecanone, thus cyclododecanone oxime obtained.Butanone is preferred non-annularity alkane ketone; Make subsequently Diacetylmonoxime.
Particularly, the invention still further relates to the method for preparing cyclohexanone-oxime, it comprises the azanol that the method according to this invention is obtained and reacts with pimelinketone.The method can be carried out in a manner known way, and for example in the above described in definite prior art, its content relevant with felicity condition is incorporated to this paper by reference.
(ring-type) oxime obtained according to the present invention particularly can be for the preparation of lactan.This can reset by Beckmann in a manner known way.
Therefore, the cyclohexanone-oxime obtained according to the present invention can be for the preparation of hexanolactam.Therefore, the invention still further relates to the method for preparing hexanolactam, the method comprises the cyclohexanone-oxime that the method according to this invention is obtained and carries out the Beckmann rearrangement, thereby forms hexanolactam.The preparation of hexanolactam can be carried out in a manner known way, and for example in the above described in definite prior art, its content relevant with suitable condition is incorporated to this paper by reference.
Similarly, in an embodiment of the invention, by following method, obtain laurolactam, the method comprises the cyclododecanone oxime will obtained according to the present invention and carries out the Beckmann rearrangement, thereby forms laurolactam.This preparation process also can be carried out in a manner known way.
Preparation (ring-type) oxime is incorporated in single factory usually such as the method for cyclohexanone-oxime and the method for preparing lactan such as hexanolactam by it if necessary, wherein in continuous process, prepares azanol, oxime and lactan if necessary.
Now by following embodiment, present method is described.
Embodiment
Embodiment 1-5
Nitrate reduction carries out in industrial gas lift loop reactor, and this reactor is by inflating rising part, liquid-gas separate part, gas re-circulation part, using the part circulating liquid as product, (wherein measuring concentration shown in table 1; These concentration are corresponding to the concentration in conversion zone) from the filtration fraction containing separating the liquid reactor of catalyzer, form.Be fed in reactor by fresh hydrogen and use gas purging, so that maintain about 1.4MPa in the hydrogen dividing potential drop of the top area of reactor.Average reactor temperature maintains approximately 50 ℃.Use the Pd/C of 10 % by weight as catalyzer.Add approximately 45 gram GeO
2as activator.Catalyzer based on being present in the inorganic treating liquid body in reactor (take and do Pd/C) concentration is about 1 % by weight.The feeding rate and the feed composition that are fed to the inorganic treating liquid body of reactor change in wide scope, as shown in table 1, and this causes the composition of reactor product different different with the azanol throughput rate.Table 1 has been listed the performance data at the lower nitrate reduction reactor of reference conditions (' Plant ref. '), with (wherein reduced nitrate concentration and nitrate and phosphatic ratio in the method according to this invention, the performance data of nitrate reduction reactor and the numerical value of the ratio of the ammonia of combination rising and nitrate) (' E1 ' to ' E5 ', and comprise ' E5 ') the two.The amount of the catalyzer (to do Pd/C) in the inflation elevated areas of the activity in table 1 based on being present in hydrogenation reactor.In table 1 ' E1 ' enumerated the composition of inorganic liquid product to ' E5 ' and comprise ' E5 ', be shown in table 2 forming of inorganic liquid product that 7 experiments providing in US-6759556 (wherein Tc is measured by the inventor) obtain, the two can have been compared.
Table 1: at reference conditions and the nitrate concentration and the nitrate of reduction and the plant experiment under the phosphoric acid salt ratio that are reducing.
PO
4=total phosphate
Comparative Examples 1-7
Table 2: form according to the liquid of the reactor of the nitrate reduction for high azanol concentration of US-6759556.
PO
4=total phosphate
Comparative Examples 8-10
Prepare product mixtures, carry out the impact of analog product concentration on the resulting ctystallizing point of product mixtures.Regulate the composition of product mixtures, make key property numerical value as H
+with buffering, compare at desired level, and NO
3 -concentration can be predicted on the level of high reaction rate those of ordinary skills.Table 3 shows, except now with relatively high NO
3 -concentration, relatively high NO
3 -with phosphate radical ratio and relative low NH
4 +with NO
3 -in the processing window of other aspect routines of ratio, with the result shown in table 1, compare, the Tc of product mixtures raises along with the rising of azanol production concentration.It should be pointed out that Tc preferably should be controlled at lower than 25 ℃ and particularly lower than 20 ℃ for suitable factory's operation.Result shown in table 3 has shown, under the condition of the expected high reaction rate level of those skilled in the art, with high azanol concentration operation, usually can cause the crystallization risk to increase.
Table 3: at NH
4 +/ NO
3 -in the processing window of<2.2mol/mol, increase the example of azanol production concentration on the impact of the Tc of product mixtures.
PP
4=total phosphate radical
Claims (15)
1. a method for preparing azanol in successive processes, it comprises the nitrate in acidic aqueous liquid and phosphoric acid salt is fed to conversion zone and uses hydrogen reduction nitrate, thereby formation azanol, wherein control described nitrate and phosphatic charging, described hydrogen and temperature, so that be less than 1.0mol/kg in the concentration of nitrate described in described conversion zone, the concentration of described nitrate records in leaving the liquid of described conversion zone; In described conversion zone, nitrate and phosphatic mol ratio are 0.5 or less; And the mol ratio of ammonia and nitrate is in 2.2 to 7 scope.
2. the method for claim 1, the mol ratio of wherein said ammonia and nitrate is in 2.3 to 6 scope, particularly in 2.5 to 5 scope.
3. method as claimed in claim 1 or 2, the concentration of wherein said nitrate is in 0.3 to 0.9mol/kg scope, particularly in 0.4 to 0.8mol/kg scope.
4. as claim 1,2 or 3 described methods, wherein nitrate and phosphatic mol ratio are in 0.1 to 0.4 scope, particularly in 0.10 to 0.30 scope.
5. method as described as any one in the claim of front, wherein in described conversion zone buffering than in 0.4 to 0.8 scope, particularly in 0.45 to 0.70 scope, more specifically in 0.50 to 0.65 scope.
6. method as described as any one in the claim of front, the preparation of wherein said azanol carrys out catalysis by palladium-containing catalyst.
7. method as claimed in claim 6, wherein said catalyzer is provided on carbon support.
8. method as described as claim 6 or 7, wherein said catalyzer also comprises platinum.
9. method as described as any one in the claim of front, wherein the H+ volumetric molar concentration in 0.4 to 0.8mol/kg scope, particularly in 0.45 to 0.70mol/kg scope, more specifically in 0.50 to 0.65mol/kg scope.
10. method as described as any one in the claim of front, the temperature in wherein said conversion zone in 20 to 70 ℃ of scopes, preferably in 30 to 60 ℃ of scopes, particularly in 35 to 55 ℃ of scopes.
11. the method for the preparation of oxime, it comprises method as described as any one in the claim of front, subsequently by described azanol and alkane reactive ketone, particularly with the alkane reactive ketone of the group that is selected from pimelinketone, cyclododecanone and butanone.
12. method as claimed in claim 11, wherein said alkane ketone is pimelinketone, and described oxime is cyclohexanone-oxime.
13. the method for the preparation of hexanolactam, it comprises method as claimed in claim 12, subsequently described cyclohexanone-oxime is carried out to the Beckmann rearrangement.
14. method as claimed in claim 11, wherein said alkane ketone is cyclododecanone, and described oxime is cyclododecanone oxime.
15. the method for the preparation of laurolactam, it comprises method as claimed in claim 14, subsequently described cyclododecanone oxime is carried out to the Beckmann rearrangement.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11163580 | 2011-04-22 | ||
| EP11163580.1 | 2011-04-22 | ||
| PCT/EP2012/056923 WO2012143330A1 (en) | 2011-04-22 | 2012-04-16 | Method for preparing hydroxylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103492312A true CN103492312A (en) | 2014-01-01 |
| CN103492312B CN103492312B (en) | 2016-11-02 |
Family
ID=44209969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280019822.3A Active CN103492312B (en) | 2011-04-22 | 2012-04-16 | The method preparing azanol |
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| Country | Link |
|---|---|
| KR (1) | KR101904568B1 (en) |
| CN (1) | CN103492312B (en) |
| TW (1) | TW201247527A (en) |
| WO (1) | WO2012143330A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836353A (en) * | 2017-11-27 | 2019-06-04 | 黄飞熊 | The method of optimization manufacture cyclohexanone oxime |
| CN113735076A (en) * | 2021-09-14 | 2021-12-03 | 宁波四明化工有限公司 | Method for preparing hydroxylamine salt |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115092897B (en) * | 2022-07-21 | 2023-07-14 | 河北工业大学 | Method for preparing hydroxylamine by catalyzing cyclohexanone oxime hydrolysis through vinyl modified silicon dioxide grafted acidic polymeric ionic liquid |
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| CN101218171A (en) * | 2005-07-08 | 2008-07-09 | 帝斯曼知识产权资产管理有限公司 | Hydroxylammonium continuous production process |
| EP1947056A1 (en) * | 2007-01-05 | 2008-07-23 | China Petrochemical Development Corporation | Recycling system for hydroxylamine formation and oximation |
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| BE1009767A3 (en) * | 1995-11-10 | 1997-08-05 | Dsm Nv | Process for the preparation of hydroxylammonium. |
| MXPA02011962A (en) | 2000-06-05 | 2003-07-14 | Dsm Nv | Process for the production of cyclohexanone oxime. |
| CN1203050C (en) | 2000-06-05 | 2005-05-25 | Dsmip财产有限公司 | Process for production of cyclohexanone oxime |
| ES2410810T5 (en) | 2002-01-16 | 2022-02-18 | Ube Industries | Processes for producing laurolactam from cyclododecanone |
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- 2012-04-16 KR KR1020137027597A patent/KR101904568B1/en active IP Right Grant
- 2012-04-16 WO PCT/EP2012/056923 patent/WO2012143330A1/en active Application Filing
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| CN1741987A (en) * | 2003-01-30 | 2006-03-01 | 帝斯曼知识产权资产管理有限公司 | Processing contains the method for the organic solution of cyclohexanone-oxime, pimelinketone and organic solvent |
| CN101218171A (en) * | 2005-07-08 | 2008-07-09 | 帝斯曼知识产权资产管理有限公司 | Hydroxylammonium continuous production process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836353A (en) * | 2017-11-27 | 2019-06-04 | 黄飞熊 | The method of optimization manufacture cyclohexanone oxime |
| CN113735076A (en) * | 2021-09-14 | 2021-12-03 | 宁波四明化工有限公司 | Method for preparing hydroxylamine salt |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201247527A (en) | 2012-12-01 |
| WO2012143330A1 (en) | 2012-10-26 |
| KR20140012146A (en) | 2014-01-29 |
| CN103492312B (en) | 2016-11-02 |
| KR101904568B1 (en) | 2018-10-04 |
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