CN103359696B - A kind of method of continuous production hydroxylammonium - Google Patents
A kind of method of continuous production hydroxylammonium Download PDFInfo
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Abstract
A kind of method of continuous production hydroxylammonium, the method comprises the following steps: purify gas；Purification gas is separated into a) waste gas and b) recyclegas, i) b) mol ratio of the hydrogen in recyclegas and d) fresh hydrogen in the range of 50: 50 90: 10；Ii) purify the concentration of hydrogen in gas and be greater than 30% volume and less than 80% volume and iii) wherein recyclegas line there are gas recycle compressor and gas recycle compressor to have the compression ratio in the range of 1.01 to 1.4.
Description
Technical field
The present invention relates to one in hydroxyl ammonium salt synthesis zone to have the selective continuous process of higher hydroxylammonium
The method preparing hydroxylammonium, it includes being recycled in the purification gas of hydroxyl ammonium salt synthesis zone by control
Hydrogen makes hydrogen in purification gas dense with the molar ratio of the fresh hydrogen being added into hydroxyl ammonium salt synthesis zone
Degree is more than 30% volume.
Background technology
The important use of hydroxyl ammonium salt is for preparing oxime from ketone or aldehyde, particularly being prepared hexamethylene by Ketohexamethylene
Ketoxime.For the preparation of this oxime, in known circulation method, aqueous acidic buffer reaction medium
Circulation is kept in hydroxyl ammonium salt synthesis zone and oxime synthesis zone.Reaction medium by such as phosphoric acid and/or sulphuric acid and this
The buffer salt that a little acid derive, such as basic salt and/or ammonium salt acidic buffer.In hydroxyl ammonium salt synthesis zone,
With hydrogen, nitrate ion or nitrogen oxides in circulation inorganic liquid are transformed into azanol.
Input fresh hydrogen is to hydroxyl ammonium salt synthesis zone, and periodic purge goes out a certain amount of gas from system
With the hydrogen partial pressure that maintenance is constant.Purify gas and include the noble gas component in fresh hydrogen and generation
Gaseous by-product nitrogen (N2) and nitrous oxide (N2O)。
Azanol reacts the corresponding hydroxyl ammonium salt of formation with free buffering acid, subsequently this hydroxyl ammonium salt is inputted oxime
Synthesis zone, it generates corresponding oxime with reactive ketone there, discharges acid simultaneously.Divide from reaction medium
After separating out oxime, reaction medium is recycled to hydroxyl ammonium salt synthesis zone and in reaction medium, adds new nitre
Acid ion or nitrogen oxides.
In the case of synthesizing hydroxyl ammonium salt with phosphoric acid and nitrate solution, above-mentioned chemical reaction represents such as
Under:
Reaction 1) prepare hydroxylammonium in hydroxyl ammonium salt synthesis zone；
2H3PO4+NO3 -+3H2→NH3OH++2H2PO4 -+2H2O
Reaction 2) prepare oxime in oxime synthesis zone:
Reaction 3) isolate formation oxime after, with HNO3Form supplement new nitrate ion:
H3PO4+H2PO4 -+HNO3+3H2O→2H3PO4+NO3 -+3H2O
First reaction is heterogeneous catalysis.Preferably, catalyst is with the shape of homodisperse solid
Formula exists as the dispersion phase in liquid reaction mixture.
The mixture of reaction products of the first step is the suspended substance Han solid catalyst particle in hydroxylammonium salt solution
Aqueous inorganic process liquid.
From course of reaction, inorganic process liquid can contain intermediate material, such as azanol or ammonia,
It also can be protonated as such as hydroxylammonium or ammonium.It is to say, according to azanol of the present invention and hydroxylammonium all
Can be understood as azanol and/or hydroxylammonium, ammonia and ammonium can be understood as ammonia and/or ammonium simultaneously.
Before this aqueous inorganic process liquid is input to oxime synthesis zone (reaction 2), preferably
Solid catalyst particle is isolated from this aqueous inorganic process liquid.After filtration, this inorganic process liquor
Body is hydroxylammonium salt solution filtrate.
Such process includes DSM'sProcess is (see, for example H.J.Damme, J.T.van
Goolen and A.H.de Rooij, Cyclohexanone oxime made without by-product
(NH4)2SO4, July10,1972, Chemical Engineering；pp54/55or Ullmann′s
Encyclopedia of Industrial Chemistry(2005)at page6/7under chapter
Caprolactam)。
Although the preparation of hydroxylammonium in decades is known and the known preparation method of improvement is ground the most
Study carefully for many years, but the existing commercial run with persistence yet suffers from deficiency.
Particularly, during known continuous print, to changing into side-product ammonium, N2O and N2's
Selectivity is a difficult problem.
Side-product can be formed according to following equation:
NO3 -+2H++4H2→NH4 ++3H2O
2NO3 -+2H++4H2→N2O+5H2O
2NO3 -+2H++5H2→N2+6H2O
Additionally, the selectivity generating by-product improves along with the carrying out of reaction.This causes to obtain
One preferable hydroxylammonium productivity ratio, compared with the consumption in the reaction 1 of the formation with hydroxylammonium, needs to increase
Add the amount of compound (nitrate, hydrogen) in reactor.It is therefore desirable to ' hydroxylammonium selectivity '
In decrement compensate.
' hydroxylammonium selectivity ' used herein (selectivity to the product of hydroxylammonium) is defined as: hydroxyl
2 times of the amount of hydroxyl ammonium that ammonium salt synthesis zone produces consume H with hydroxyl ammonium salt synthesis zone+The mol ratio of amount.Change and
Yan Zhi, is hydroxylammonium product and proton (H+) mol ratio that consumes, one of them hydroxylammonium needs two protons
(H+).Low hydroxylammonium selectivity means that more undesirable by-product can produce.Low hydroxylammonium is selective
Definition is that hydroxylammonium selectivity is less than 70%.
It is known that it is by reducing temperature of reactor and or optimizing that hydroxylammonium optionally increases
GeO2The ratio of/Pd realizes, and optimizes GeO2The ratio of/Pd can make the activity of catalyst reduce but select
Property improve.
But, reduce temperature of reactor somewhat expensive, because it needs temperature to be cooled to close to normal
The temperature of cooling water.
Only improving the volume of the catalyst adding hydroxyl ammonium salt synthesis zone to, efficiency is the highest, because its meeting
Block the filter of hydroxyl ammonium salt synthesis zone and add cost.
EP1275616 discloses the method preparing hydroxylammonium, by containing hydrogen and non-hydrogen in the method
The admixture of gas of gaseous compound is discharged from reactant mixture and is subsequently isolated out the most non-
The gaseous compound of hydrogen is to obtain rich in hydrogen gas, and this gas returns to hydrogenation reaction zone subsequently.
But, the method needs a complicated separation process and hydroxylammonium selectivity the most relatively low.
US20050047987A1 relates to a kind of method preparing hydroxylammonium, and the method includes following step
Rapid:
A. in reactant mixture, add Gaseous Hydrogen, anti-containing aqueous in reactant mixture
Answer medium and gas phase；
B. in described reactant mixture, with hydrogen catalysis reduction nitrate or nitrogen oxides
Form hydroxylammonium；
C. taking out admixture of gas from reactant mixture, this admixture of gas contains gas
State hydrogen and the non-hydrogen of gaseous state；
D. from admixture of gas, the non-hydrogen of at least part of gaseous state is isolated to obtain
To the gas rich in hydrogen；
E. the gas that will be enriched in hydrogen is input to hydrogenation zone.
The deficiency of described method is specific separator of should installing and operate, its can by non-hydrogen from
Admixture of gas is separated.It describe this gas separate can pass through membrance separation, pressure-variable adsorption and
Low temperature distillation completes.All these technology are required to specific instrument to separate hydrogen and non-hydrogen.
Described equipment is complicated, expensive and consume energy (such as energy, steam).
Therefore, it is an object of the invention to provide a kind of method preparing hydroxylammonium in continuous process, the party
The problem that the alternative known method of method overcomes hydroxylammonium optionally to reduce.
Summary of the invention
Inventor surprisingly it has been found that, be recycled to hydrogen in the purification gas of hydroxyl ammonium salt synthesis zone by control
H in hydroxyl ammonium salt synthesis zone can be improved with the mol ratio of the fresh hydrogen joining hydroxylammonium synthesis zone2's
Dividing potential drop, and then improve hydroxylammonium selectivity.H in reactor2Dividing potential drop is the highest, the most hydrogen and nitrate
Or conversion of nitrogen oxides be hydroxylammonium and the volume of noble gas that produces the least.H in reactor2's
Dividing potential drop shows as purifying H in gas2Volume %.
H in reactor is improved for balance2Dividing potential drop impact, can take to include to optimize GeO2/Pd
The ratio of [mg/gr]；Reduce catalyst concn simultaneously；Reduce the method for temperature of reactor and several simultaneously
The combination of method, likely accomplishes real cost-effective by said method.
By increasing H2Dividing potential drop (reduce temperature or reduce GeO2Consumption) catalyst that causes lives
The loss of property can be compensated.
It is a further object of the invention that, with the traditional method implemented in identical production equipment
Comparing, what preparation had that higher hydroxylammonium maintains certain hydroxylammonium productivity ratio the most simultaneously prepares hydroxylammonium
Method.Relative in identical production equipment implement traditional method, the method will be one more
Environmental protection and the method more saved.
Therefore, the invention provides a kind of at a reactor with top region and hydroxyl ammonium salt synthesis zone
The method preparing hydroxylammonium the most continuously, wherein hydroxyl ammonium salt synthesis zone includes liquid phase, gas phase and heterogeneous hydrogen
Changing catalyst, wherein in this hydroxyl ammonium salt synthesis zone, nitrate hydrogenation forms hydroxylammonium (NH3OH+), ammonium
(NH4 +), nitrogen (N2) and nitrous oxide (N2O), the method comprise the steps that
I) at top region collection and purification gas；
II) purification gas is separated into a) waste gas and b) recyclegas；
III) fresh hydrogen is joined b) in recyclegas to produce c) rich in hydrogen gas and by c)
Hydroxyl ammonium salt synthesis zone is returned to rich in hydrogen gas；And/or
IV) d) fresh hydrogen is incorporated into hydroxyl ammonium salt synthesis zone；And/or
V) by recyclegas line, b) recyclegas is incorporated into hydroxyl ammonium salt synthesis zone；
It is characterized in that:
I) b) mol ratio of the hydrogen in recyclegas and d) fresh hydrogen 50: 50-90: 10 scopes
In；
Ii) purify the concentration of hydrogen in gas and be greater than 30% volume and less than 80% volume；With
Iii) gas recycle compressor and gas recycle compressor is wherein had to have 1.01 in recyclegas line
Compression ratio in the range of 1.4.
Therefore, great majority purification gas is circulated.
Preferably, b) mol ratio of the hydrogen in recyclegas and d) fresh hydrogen 60: 40-85: 15
In the range of, most preferably 65: 35-80: 20.
Preferably, ii) to purify the concentration of hydrogen in gas be more than 35% volume, the most greatly
In 40% volume, especially greater than 45% volume.Preferably, ii) purify the concentration of hydrogen in gas and be
Less than 70% volume.
In purification gas, the concentration of hydrogen need not be identical with the concentration of hydrogen in reactor.
Preferably, d) fresh hydrogen contains the hydrogen (H of 85-99.95% volume2).Fresh hydrogen often contains
There is the noble gas of at least 500ppm (=0.05% volume).Preferably, d) fresh hydrogen contains low
Noble gas in 15% volume.
If producing c) rich in hydrogen gas by step III, preferably contain 34-rich in hydrogen gas
The hydrogen of 90% volume.
Preferably, the d of 0.1-45% volume c) is contained rich in hydrogen gas) fresh hydrogen and 55-
The b of 99.9% volume) recyclegas.
It is highly preferred that c) contain the d of 5-30% volume rich in hydrogen gas) fresh hydrogen and 70-95%
The b of volume) recyclegas.It is highly preferred that c) contain the d of 10-25% volume rich in hydrogen gas) new
Fresh hydrogen and the b of 75-90% volume) recyclegas.
Preferably, in a) waste gas, nitrogen (N2) and nitrous oxide (N2O) mol ratio is at least
5∶1。
Inventor finds, compared with in purification gas, density of hydrogen is less than the method for 30% volume, with nitre
The time lengthening of hydrochlorate hydrogenation, hydroxylammonium optionally declines and is compensated.
Fresh hydrogen can be input to hydroxyl with concentration (Hydrogen Vapor Pressure) known per se in some way
Ammonium salt synthesis zone.Preferably, hydrogen partial pressure minimum in hydroxyl ammonium salt synthesis zone is maintained at least 1.0
MPa.Generally, in hydroxyl ammonium salt synthesis zone, average hydrogen dividing potential drop is less than 10MPa.
It is well known in the art that, the density of hydrogen being typically based in gas phase, purify the hydrogen in gas dense
Degree can be monitored and controlled within the limits prescribed well.This gas phase is to purify from hydroxyl ammonium salt synthesis zone
Going out, density of hydrogen is to utilize hydrogen gas detector to record.Generally, for easy to operate, generally divide
Density of hydrogen in analysis a) waste gas, because a) composition of waste gas is identical with purifying gas.
When density of hydrogen is beyond prescribed limit, a) useless by adding d) fresh hydrogen regulation to reactor
Hydrogen volume in gas also regulates a) waste gas: the b) ratio of recyclegas.
In a specific embodiment, before b) recyclegas enters hydroxyl ammonium salt synthesis zone, add d)
Fresh hydrogen is in b) recyclegas.
In another embodiment, in course of reaction, d) fresh hydrogen is entered from multiple positions
Enter reactor, such as the cooler described in US2007/0231240 above and below.
Preferably, introduce d) fresh hydrogen at least to enter into reactor from 2 different positions.
Surprisingly it has also been found that the certain compression that gas recycle compressor has in recyclegas line
Provide a kind of improved method preparing hydroxylammonium in a continuous process.The compression ratio of gas recycle compressor is determined
Justice is absolute outlet pressure and the ratio of absolute intake pressure of gas recycle compressor.
Preferably, in the range of in recyclegas line, the compression ratio of gas recycle compressor is 1.01 to 1.4,
More preferably 1.03 to 1.25, most preferably 1.05 to 1.15.
The catalyst used in preparation hydroxyl ammonium salt is mainly made up of the metal selected from platinum family, is such as positioned at
Such as on carbon carrier using palladium or (palladium+platinum) as the catalyst of active component.Can be by having one
Plant or multiple catalysts activator activates this catalyst.Catalyst activator can be selected from copper, silver,
Cadmium, hydrargyrum, gallium, indium, thallium, germanium, stannum, lead, arsenic, antimony and bismuth.Most preferably, this catalyst is lived
Agent is germanium.
Preferably, use catalyst and the compositions of catalyst activator, such as, include GeO2/ Pd group
Compound.
Preferably, the content of this catalyst activator is that 0.01-100mg/g catalyst is (on carrier mass
Active component), preferably 0.05-50mg/g catalyst, more preferably 0.1-10mg/g urges
Agent, most preferably 1-7mg/g catalyst.
Containing the compound of described element, such as oxide, nitrate, phosphate, sulfate, halogenation
Thing and acetate are also used as catalyst activator.Element as described in US3767758 or they
Compound, can be directly as catalyst or be added in reaction medium.
The catalyst that (reaction 1) uses in preparing hydroxylammonium salt solution, preferably comprises and is positioned on carrier
Heavy metal, the platinum being preferably placed on carrier (Pt), palladium (Pd) or platinum and palladium compositions.
Although normally tending to use pure palladium, but pure palladium may be containing certain platina matter, in pure palladium
Palladium: the part by weight of platinum can be different.Preferably palladium contains the platinum less than 25wt%, more preferably
Less than 5wt%, the platinum of even more preferably below 2wt%, especially preferably less than 1wt%.
Preferably, carrier includes carbon (such as graphite, carbon black, or activated carbon) or carrying alumina
Body, more preferably graphite or activated carbon.The catalyst used in hydroxyl ammonium salt synthesis zone preferably comprises 1-
The heavy metal of the heavy metal of 25wt%, more preferably 5-15wt%, relative to carrier and the gross weight of catalyst
Amount.
As a rule, the consumption of the catalyst in hydroxyl ammonium salt synthesis zone is 0.05-25wt%, is preferably
0.2-15wt%, more preferably 0.5-5wt%, relative to the inorganic process liquor in hydroxyl ammonium salt synthesis zone
Body gross weight.
The particle mean size of catalyst granules is generally 1-150 μm, preferably 2-100 μm, more preferably
Be 3-60 μm, most preferably 5-40 μm.So-called " particle mean size " refers to 50vol%'s
Granule is more than nominal diameter.
Generally, prepare hydroxylammonium temperature of reactor more than 20 DEG C, more preferably 30 DEG C with
On, especially more than 35 DEG C.Generally, hydroxylammonium is prepared at temperature of reactor less than at 70 DEG C, preferably
Be less than 65 DEG C especially less than 60 DEG C.
Can be any reactor being suitable for for preparing the production equipment of hydroxylammonium, such as, there is machine
The reactor of tool agitator or bubble column, more preferably bubble column.NL6908934 describes conjunction
The example of suitable bubble column.
The typical reactor configurations preparing aqueous hydroxylammonium salt solution and separation solid catalyst particle is tool
There is the hydrogenation bubble-column reactor of cooling segment.Reactor configurations usually includes that the gas much organized separates
Pipe and filter tube.
Accompanying drawing explanation
Accompanying drawing 1 and accompanying drawing 2 describe a kind of typical production preparing hydroxylammonium and recyclegas and
Add the different embodiments of fresh hydrogen.Including reactor tube (1), cooling element (2), gas circulation pressure
Contracting machine (3) and purification plenum zone (4).Line (5) is inorganic liquid circulating ring.Line (a) is a) waste gas,
Line (b) is b) recyclegas.Line (c) is c) rich in hydrogen gas, and line (d) is d) fresh hydrogen.
In accompanying drawing 1, interpolation d) fresh hydrogen is joined by line (d1) and obtains c in recyclegas) rich in
Hydrogen gas, line (c).Or, directly added by line (b) b) that recyclegas is not to reaction tube
Add fresh hydrogen.Simultaneously can also pass through line (d2) and directly add d) fresh hydrogen to reaction tube with or
Add cooling element top to by line (d3), and or add cooling element bottom to by line (d4).
In accompanying drawing 2, directly added by line (b) b) recyclegas to reactor tube (1).Can also be direct
D is added by line (d2)) fresh hydrogen is to reaction tube, and or added on cooling element by line (d3)
Portion, and or add cooling element bottom to by line (d4).Can also directly add recyclegas to cold
But member upper or bottom, is directly appended to reactor tube (1) in addition or selectively.
The present invention is further illustrated by below example, but is not limited to this.
Embodiment
Embodiment 1-6
Carrying out the production of hydroxylammonium in equipment, this equipment usesTechnology.At hydrogenation
In device, along with in the water-bearing phosphate containing buffer solution, nitrate is optionally converted into hydroxylammonium, produce
Side-product ammonia, N are given birth to2O and N2。
The condition of pin hydrochlorate hydrogenation reactor is:
Mean temperature: 35-60 DEG C
Reactor pressure: 2.0-3.0MPa.
Activator type: GeO2
Activator/catalyst ratio: 3-7gr GeO2/ kg catalyst
The compression ratio of gas recycle compressor is in the range of 1.05 to 1.2.
For catalyst type, d) fresh hydrogen component, dry a) waste gas component, in recyclegas b)
The d of hydrogen sum) mol ratio of fresh hydrogen and hydroxylammonium selectivity, as shown in table 1.
By by the d of the hydrogen sum in recyclegas b)) mol ratio of fresh hydrogen maintains 50: 50-
In the range of 90: 10；And ensure to purify the concentration of hydrogen in gas and more than 30% volume and be less than 80%
Volume, so that it may be remained above the hydroxylammonium selectivity of 75%.
Table 1
Claims (7)
1. in a reactor with top region and hydroxyl ammonium salt synthesis zone, prepare hydroxylammonium continuously for one kind
Method, wherein hydroxyl ammonium salt synthesis zone includes liquid phase, gas phase and heterogeneous hydrogenation catalyst, wherein should
In hydroxyl ammonium salt synthesis zone, nitrate hydrogenation forms hydroxylammonium (NH3OH+), ammonium (NH4 +), nitrogen (N2) and
Nitrous oxide (N2O), the method comprise the steps that
I) at top region collection and purification gas；
II) purification gas is separated into a) waste gas and b) recyclegas；
III) fresh hydrogen is joined b) in recyclegas to produce c) rich in hydrogen gas and by c)
Hydroxyl ammonium salt synthesis zone is returned to rich in hydrogen gas；And/or
IV) d) fresh hydrogen is incorporated into hydroxyl ammonium salt synthesis zone；And/or
V) by recyclegas line, b) recyclegas is incorporated into hydroxyl ammonium salt synthesis zone；
It is characterized in that:
I) b) mol ratio of the hydrogen in recyclegas and d) fresh hydrogen in the range of 50:50-90:10；
With
Ii) purify the concentration of hydrogen in gas and be greater than 30% volume and less than 80% volume；With
Iii) wherein recyclegas line has gas recycle compressor and gas recycle compressor have 1.01 to
Compression ratio in the range of 1.4；
Iv) wherein the minimum hydrogen partial pressure of hydroxyl ammonium salt synthesis zone is maintained at least 1.0MPa；And
V) d) fresh hydrogen contains the noble gas less than 15% volume.
Method the most according to claim 1, wherein temperature of reactor is less than 70 DEG C.
Method the most according to claim 1, wherein uses the catalyst containing Pd and GeO2Catalyst
Activator.
Method the most according to claim 1, wherein purifies density of hydrogen in gas and is greater than 35% volume
And less than 70% volume.
Method the most according to claim 1, wherein nitrogen (N in waste gas2): nitrous oxide (N2Rubbing O)
Your ratio is at least 5:1.
Method the most according to claim 1, wherein can obtain the hydroxylammonium selectivity of at least 70%.
Method the most according to claim 1, in the range of wherein gas recycle compressor has 1.03 to 1.25
Compression ratio.
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| CN201310109187.4A CN103359696B (en) | 2012-03-31 | 2013-03-29 | A kind of method of continuous production hydroxylammonium |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3767758A (en) * | 1967-12-14 | 1973-10-23 | Stamicarbon | Process for the preparation of salts of hydroxylamine |
| CN100469758C (en) * | 2006-04-05 | 2009-03-18 | 中国石油化学工业开发股份有限公司 | Method for preparing hydroxylamine |
-
2013
- 2013-03-29 CN CN201310109187.4A patent/CN103359696B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3767758A (en) * | 1967-12-14 | 1973-10-23 | Stamicarbon | Process for the preparation of salts of hydroxylamine |
| CN100469758C (en) * | 2006-04-05 | 2009-03-18 | 中国石油化学工业开发股份有限公司 | Method for preparing hydroxylamine |
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