CN105418454A - Industrial scaled continuous method for producing oxime - Google Patents
Industrial scaled continuous method for producing oxime Download PDFInfo
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- CN105418454A CN105418454A CN201410475469.0A CN201410475469A CN105418454A CN 105418454 A CN105418454 A CN 105418454A CN 201410475469 A CN201410475469 A CN 201410475469A CN 105418454 A CN105418454 A CN 105418454A
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Abstract
The invention relates to an industrial scaled continuous method for producing oxime. Oxime is produced by circulating an inorganic process liquid in an oxime synthetic region and a hydroxylamine synthetic region, wherein the molybdenum content in the inorganic process liquid leaving the hydroxylamine synthetic region is 0.3 ppm (weight/weight) to 2 ppm (weight/weight).
Description
Technical field
The present invention relates to a kind of commercial scale continuous method of producing oxime, wherein prepare oxime by azanol and aldehydes or ketones reaction.Especially, it refers to foundation
technology is by the method for pimelinketone and azanol continuous seepage cyclohexanone-oxime.
Background technology
Well-known cyclohexanone-oxime can be prepared according to different technologies, as NO reduction technique in oximes technology, HSO technology, sulfuric acid and
technology.
In general,
technology is that optimization technique combines the production of high quality cyclohexanone-oxime because of it, to the highly selective of azanol, confirms that every production line easily extensible can not produce any byproduct of ammonium sulfate at least 200kat (annual kiloton).
According to
technology prepares cyclohexanone-oxime in circulation technology, and wherein said water-containing reacting medium (inorganic process liquid) keeps circulation in hydroxylammonium synthesis zone and oxime synthesis district.Add fresh hydrogen to hydroxylammonium synthesis zone and regularly from system, give off a small amount of air to maintain a constant hydrogen dividing potential drop.The air given off contains the gaseous by-product nitrogen (N of noble gas component in hydrogen, fresh hydrogen and generation
2) and nitrogen oxide (N
2o).
The buffering salt that described water-containing reacting medium (inorganic process liquid) derives by such as phosphoric acid and/or sulfuric acid and these acid, such as basic salt and/or ammonium salt acidic buffer.In hydroxylammonium synthesis zone, with gaseous hydrogen, nitrate ion or nitrogen oxide in the inorganic process liquid of circulation are transformed into azanol.
In hydroxylammonium synthesis zone, nitrate ion or nitrogen oxide prepare azanol with hydrogen reaction in the solution, and subsequently by this azanol input cyclohexanone-oxime synthesis district, it and pimelinketone react and generate cyclohexanone-oxime there.Isolate cyclohexanone-oxime from water-containing reacting medium (inorganic process liquid) after, water-containing reacting medium (inorganic process liquid) is recycled to hydroxylammonium synthesis zone and adds fresh nitrate ion or nitrogen oxide in water-containing reacting medium (inorganic process liquid).
When with phosphoric acid and nitrate solution synthesizing hydroxyamine, chemistry side should be expressed as follows:
Reaction 1) prepare azanol in hydroxylammonium synthesis zone;
2H
3PO
4+NO
3 -+3H
2→NH
3OH
++2H
2PO
4 -+2H
2O
Reaction 2) prepare cyclohexanone-oxime in cyclohexanone-oxime synthesis district;
Reaction 3) add HNO
3with supplementary nitrate ion:
H
3PO
4+H
2PO
4 -+HNO
3+3H
2O→2H
3PO
4+NO
3 -+3H
2O
First reaction is heterogeneous catalysis.Preferably, catalyzer exists using the form of homodisperse solid as the disperse phase in liquid reaction mixture.Preferably, described catalyzer is the catalyzer containing Pd on carbon support.
The inorganic process liquid (IPL) obtained in first reaction is the aqueous solution containing the ammonium phosphate buffer liquid with different concentration hydroxyl ammonium salt and nitrate.
From reaction process, inorganic process liquid can contain intermediate material, such as hydroxylammonium or ammonia, and it also can be protonated as such as azanol or ammonium.That is, can be interpreted as hydroxylammonium and/or azanol according to hydroxylammonium of the present invention and azanol, ammonia and ammonium can be understood as ammonia and/or ammonium simultaneously.
Before this inorganic process liquid (IPL) being input to cyclohexanone-oxime synthesis district (reaction 2), preferably from this moisture inorganic process liquid, isolate solid catalyst particle.This separation is implemented preferable through filter.After filtration, this inorganic process liquid is hydroxylammonium salt solution filtrate.Described continuous processing contains at least two loops.A loop is inorganic process liquor body loop, namely inorganic process liquid is recycled to the inorganic process liquid purification section (optionally arriving charcoal absorption district) containing extraction section and stripping zone through cyclohexanone-oxime synthesis district, then be recycled to hydroxylammonium synthesis zone through inorganic process liquid regulatory region (adding district containing an ammonolysis craft district and nitrate) at least in part, return cyclohexanone-oxime synthesis district subsequently.Second loop is organic process fluid loop, and organic process liquid is recycled to oxime purification section through oxime synthesis district, then arrives oxime recovery zone, arrives extraction section subsequently and then gets back to oxime synthesis district.Described organic process liquid contains solvent, and preferably, described solvent is toluene.Described organic process liquid can contain pimelinketone and cyclohexanone-oxime in addition, and the concentration of its cyclohexanone and cyclohexanone-oxime depends on its particular location in process.
US5364609 describes a kind of method utilizing additional step, and the ammonia that burns in this additional step generates NO, NO
2and water, be introduced in reactor and generate nitric acid simultaneously.Then nitric acid and H-H reaction are generated hydroxylammonium.N is produced between hydroxylammonium Formation period
2o and N
2gaseous by-product also creates ammonia in addition, and ammonia is dissolved in moisture inorganic process solution.NO and NO that described ammonia obtains with burning process successively
2react and form N
2gas (Piria reaction).According to described method, can avoid the detrimental accumulation of ammonia in moisture inorganic process solution, this accumulation can cause salt-pepper noise.
Also can by replacing introducing portion NO and NO by directly adding nitric acid (and ex situ formation) in this technique
2.But because the accumulation of above-mentioned ammonia, direct interpolation nitric acid can not replace completely introduces NO and NO in technique
2.
The problem of aforesaid method is that the catalyzer of reduction azanol is to poisoning very responsive, especially to metal poisoning, such as poisoning to the molybdenum (Mo) be usually present in the steel of pipeline and production reactor accessory.A.H.deRooij etc. describe and utilize 304 models but not 316 model stainless steels can solve this problem in Chemtech, Volume7, May1977, pp309-315.But in phosphatic acidic aqueous solution, phosphoric acid and nitric acid condition can cause corrosion, even if in low molybdenum steel equipment.Because molybdenum is dissolved in phosphate-containing acidic aqueous solution.
In addition, be input to the fluid in hydrogenation reactor, may molybdenum be contained as nitric acid and phosphoric acid.Well-known molybdenum is harmful to hydroxylammonium reaction preference.US3767758 describes molybdenum and reduces the selectivity of azanol and cause and create more ammonia.It is estimated that the existence of 1ppm molybdenum in phosphate-containing acidic aqueous solution can cause azanol selectivity to reduce by 2%.
' hydroxylammonium selectivity ' used herein (selectivity to the production of hydroxylammonium) or tout court ' selectivity ' is defined as: the amount of hydroxyl ammonium that reaction zone produces and reaction zone consume H
+the mol ratio of 2 times of amount.Wherein H
+for the positively charged ion of hydrogen atom.Much lower selectivity means can produce more undesirable by product.
Well known in the art, the amount introducing molybdenum to hydroxylammonium formation process is limited by the nitric acid introduced containing low levels molybdenum.
WO2013098174 describes a kind of method preparing hydroxylammonium in reaction zone with continuous processing, and it comprises and i) optionally direct the nitric acid containing < 0.1ppm molybdenum is joined reaction zone; And ii) wherein nitric acid by be substantially free of molybdenum and preferably the steel that forms of carbon-free steel form wall container in conveying, store and transfer; And iii) reaction zone is by substantially carrying out containing without in molybdenum and the container of wall that preferably carbon-free steel forms.
This area be also well known that by remove molybdenum can reduce the molybdenum concentration joining inorganic process liquid in hydroxylammonium synthesis zone.
EP2682365 describes a kind of method of continuous seepage azanol, has the alternatives removing molybdenum simultaneously.
Japanese Patent 52-051340 describes the method being reduced molybdenum content by ion exchange resin treatment inorganic liquid, this ion exchange resin has chelating and forms group, such as thioamides resin, mercaptan resin, dithio acid resin and carboxylic acid resin.Described aqueous solution is in batches or continuously through level or vertical packed bed ion exchange resin.The drawback of described technique is that loading and unloading ion-exchange material needs additional process.Owing to implementing this technique, producing required input of azanol will increase, to producing azanol and the fixed cost of product prepared thus produces negative influence.Ion exchange resin also can consume in addition, and regenerates this ion exchange resin with alkali and can make whole process complications.In view of ion exchange resin and alkali consumption, the variable cost of producing azanol and products thereof will improve.
US7399885 describes a kind of some functional amine group that utilizes and from acid buffering solution, removes the method for dissolving molybdenum to resin/polymer selective absorption.A drawback of described method is the relevant cost of complicated sorbing material.Another drawback of present method has no idea to regenerate the sorbent material be loaded into.
Finally, US4062927 describes and a kind ofly utilizes the co-precipitation of compound phosphoric acid iron ammonium to dissolve the method for molybdenum from nitrate/nitrogen oxide solution removal.Ammoniacal liquor and molysite is added to moisture inorganic process solution.The reaction medium produced needs to stir at least 15 minutes.Then ferric ammonium sulfate/molybdenum the salt obtained is separated.A drawback of described technique is the interpolation of molysite.Another drawback is the input that interpolation, precipitation, separation and the needs of the additional process equipment needed for sedimentary removal are relatively high.Especially relevant to stirring reaction medium at least 15 minutes investment.And also have the input that separation is relevant with removing throw out.These drop into producing azanol and the fixed cost of product prepared thus has negative influence.
In view of more than, target of the present invention is to provide a kind ofly prepares the method with high selectivity oxime in more efficiently more economical mode.
Inventor has found the alternative solution of molybdenum accumulation problem, and the program has another one advantage and namely avoids the increase of aforesaid method cost and complicated.They have developed a kind of method specifically, the method relate in aqueous solution by through embedded mixing equipment to inorganic process liquid only input aqueous ammonia thus obtain ammonium ferric phosphate/molybdenum coprecipitate reduce molybdenum concentration in inorganic process liquid.The ammonium ferric phosphate obtained/molybdenum coprecipitate can simply be separated from aqueous solution.In the recycling technique in producing oxime of filtrate of described acquisition.
Therefore, the invention provides a kind of commercial scale continuous method by producing oxime in oxime synthesis district and hydroxylammonium synthesis zone circulation inorganic process liquid, wherein, leaving molybdenum content in the inorganic process liquid of hydroxylammonium synthesis zone is 0.3ppm (w/w) to 2ppm (w/w), and described method adopts:
I) by the equipment formed containing molybdenum;
II) one can form the settling apparatus of ammonium ferric phosphate/molybdenum coprecipitate continuously;
III) one for removing the eliminating equipment of coprecipitate;
Wherein said method contains:
A. from circulation, get the inorganic process liquid of 0.1wt% to 25wt% circulation and it is combined with aqueous ammonia with the ejecta formed containing ammonium ferric phosphate/molybdenum coprecipitate in settling apparatus;
B. ejecta is inputted eliminating equipment from settling apparatus;
C. in eliminating equipment, be separated described coprecipitate obtain filtrate, by the inorganic process liquid of this filtrate input circulation;
Wherein settling apparatus contains an embedded mixing equipment and a stop container.
Detailed Description Of The Invention
The turnout that in the present invention, technical scale means oxime synthesis district is generally the scale (annual thousand of annual thousand; Kta).Usually, the throughput in oxime synthesis district is per year over 10,000 (10kta).Preferably, it is 25kta to 400kta.More preferably, the turnout in each oxime synthesis district is 50kta to 250kta.
Stopping container in the present invention is any one container, and the aqueous ammonia in this container and the mixture of inorganic process liquid have certain mean residence time after exporting from static mixing device.The application's stop container used does not move whipping device.
If be added into aqueous ammonia containing in molybdenum inorganic process liquid except iron also containing chromium ion, so except generating the coprecipitate of ammonium ferric phosphate/molybdenum, also can generate the coprecipitate of Plessy's green ammonium/molybdenum.These precipitations also can be got rid of by eliminating equipment.
One of source of molybdenum is equipment.Usually hydroxylammonium equipment used is prepared for making containing Mo.The circulation of the corrosion of equipment and inorganic process liquid (IPL) can cause molybdenum polution.It is existing that oneself finds that the existence of molybdenum polution can cause optionally reduction nitrate ion or nitrogen oxide reduction being become azanol.The another one source of molybdenum is the raw material added in technique, such as nitric acid and phosphoric acid.
In the application, present the method removing molybdenum by introducing aqueous ammonia in inorganic process liquid with the coprecipitate forming ammonium ferric phosphate/molybdenum from inorganic process liquid.Removed from inorganic process liquid by the coprecipitate of this ammonium ferric phosphate/molybdenum, it more effectively can prepare the hydroxylammonium of more high yield subsequently.
The inorganic process liquid stream that the present invention adopts circulates in the water-containing reacting medium between oxime synthesis district and hydroxylammonium synthesis zone.Described inorganic process liquid contains water, ammonia, iron, molybdenum, nitrate and phosphoric acid salt.In the process in hydroxylammonium synthesis zone and oxime synthesis district's circulation, described inorganic process liquid will carry out further one or more purifying technique such as extraction process, stripping process, active carbon absorption technology and/or NOx absorption technique.After living through each technique above-mentioned, the IPL composition of acquisition changes.But for the purpose of simplifying the description, still with the water-containing reacting medium that all each purification step of inorganic process liquid name obtain.
Remove the method for molybdenum
In a preferred embodiment, join the inorganic process liquid of settling apparatus and the temperature of aqueous ammonia lower than 45 DEG C, be preferably lower than 25 DEG C, more preferably lower than 20 DEG C.
Inline mixer is the equipment that can be used for continuous mixing liquid.Inline mixer is mounted in the mixing equipment in the pipeline of the liquid stream warp that will mix.Inline mixer comprises static state (or passive type) inline mixer and dynamic (or active) inline mixer.Dynamic inline mixer is usually charged by electric motor and is contained the hybrid element of one or more rotation.Static inline mixer by installing the flow pattern that baffle plate changes the liquid that will mix on path.A kind of design of static mixer is template mixing tank and an other equipment is made up of the several hybrid elements be contained in pipe (tubular) or in square casing.The pressure-losses that the required energy derive of mixing produces in flowing in embedded static mixer along with liquid.US patent 3286992 describes embedded static mixer.
In a preferred embodiment, described embedded mixing equipment is static mixer.In a preferred embodiment, inline mixer is that auger style static mixer hybrid element forms by several being contained in pipe.In the preferred embodiment of another one, embedded static mixer is made up of the three-element static mixer of DN60 pipeline internal screw type.
Described eliminating equipment can be from containing the arbitrary equipment removing coprecipitate aqueous phase.Preferably, eliminating equipment is sedimentation device, hydrocyclone or (film) filter plant.In a preferred embodiment, eliminating equipment is Induction refining strainer.In a preferred embodiment, eliminating equipment is the Induction refining strainer of an azanol synthesis.In a preferred embodiment, eliminating equipment is one
the Induction refining strainer of the azanol synthesis in technique.In a preferred embodiment, the mixture of aqueous ammonia and inorganic process liquid is incorporated into stop container after embedded mixing equipment exports, wherein aqueous ammonia and inorganic process liquid mixture stop the mean residence time of container be 1 minute within the scope of 900 minutes, be preferably 2 minutes within the scope of 400 minutes, be more preferably 3 minutes within the scope of 200 minutes, be especially 3 minutes within the scope of 90 minutes.
In one preferably embodiment, the aqueous ammonia adding settling apparatus is made up of the gaseous ammonia be dissolved in the water.Adding ammonia content in the aqueous ammonia of settling apparatus is in 0.5wt% to 10wt% scope, more preferably, in 1wt% to 5wt% scope.
In one preferably embodiment, the inorganic process liquid of described acquisition and the pH value (measuring at 25 DEG C) of aqueous ammonia mixture are at least 3, are preferably in 3 to 6 scopes, are more preferably in 4 to 5 scopes, most preferably are 4.6.
In one preferably embodiment, inorganic process liquid is in 1: 0.4 to 1: 4 scopes with the weight ratio of the aqueous ammonia adding settling apparatus, is more preferably in 1: 1to1: 2 scopes, is most preferably in 1: 1.2to1: 1.8 scopes.
In a preferred embodiment, the aqueous ammonia of settling apparatus is added with refrigerated water cooling.
In a preferred embodiment, the temperature of described aqueous ammonia is cooled to less than 50 DEG C, more preferably lower than 25 DEG C, even more preferably lower than 15 DEG C.
In a preferred embodiment, the temperature of inorganic process liquid is cooled to less than 50 DEG C, more preferably lower than 25 DEG C, even more preferably lower than 15 DEG C.
In a preferred embodiment, described inorganic process liquid used activated carbon treatment before input settling apparatus.
In a preferred embodiment, described inorganic process liquid used steam stripped before input settling apparatus.
In a preferred embodiment, described inorganic process liquid extracted with toluene before being input to settling apparatus.
In a preferred embodiment, the filtrate that eliminating equipment flows out is joined in steam stripped tower to remove water vapor.
In a preferred embodiment, the filtrate that eliminating equipment flows out is joined in NOx absorption equipment.
In a preferred embodiment, filtrate the joining that eliminating equipment flows out is arranged in the tank after NOx absorption equipment.
In a preferred embodiment, described oxime is cyclohexanone-oxime, cyclobutanone oxime or cyclododecanone oxime.
In a preferred embodiment, the forward direction inorganic process liquid of adding settling apparatus in inorganic process liquid adds containing molysite.
In a preferred embodiment, do not add containing molysite before inorganic process liquid joins settling apparatus.
Summary of drawings
Fig. 1 has schematically also partly set forth foundation prior art
technology produces the continuous device of cyclohexanone-oxime.
Fig. 2 schematically illustrates the method removing molybdenum according to the present invention.
Fig. 3 a has schematically also partly set forth foundation
technology produces the continuous device of cyclohexanone-oxime, and this technology removes the method for molybdenum containing with good grounds the present invention.
Fig. 3 b schematically illustrates the embodiment removing this part of molybdenum according to the present invention, and it is that foundation contains the method removing molybdenum
technology produces a part for the continuous device of cyclohexanone-oxime.
Fig. 3 c schematically illustrates another embodiment removing this part of molybdenum according to the present invention, and it is that foundation contains the method removing molybdenum
technology produces a part for the continuous device of cyclohexanone-oxime.
Accompanying drawing describes in detail
In order to simplify disclosure of the present invention, Fig. 1 schematically illustrate only part according to
technology produces the equipment of cyclohexanone-oxime and the major portion of inorganic process liquid backflow more accurately.Remainder does not show, and comprises some and relevant to organic process liquid return burns unimportant to understanding the present invention with gaseous ammonia.
As shown in Figure 1, according to
the legacy equipment that technology acticarbon produces cyclohexanone-oxime contains hydroxylammonium synthesis district [A], monoxime synthesis district [B], an extraction section [C], a stripping zone [D], a charcoal absorption district [E] and NOx uptake zone [F].
Inorganic process liquid containing phosphoric acid salt, nitrate, ammonia and azanol is left hydroxylammonium synthesis district [A] through pipeline [a] and is joined oxime synthesis district [B].In oxime synthesis district [B], pimelinketone and azanol are converted into cyclohexanone-oxime.Organic fluid containing pimelinketone and toluene synthesizes district [B] through being entered cyclohexanone-oxime by pipeline [b], and the organic fluid containing cyclohexanone-oxime and toluene of acquisition and the inorganic process liquid fluid containing phosphoric acid salt, nitrate, ammonia and different organic composition of acquisition leave cyclohexanone-oxime synthesis district [B] through pipeline [c] and [d] respectively.The organic fluid left through pipeline [c] is transported to cyclohexanone-oxime zone purification and toluene recovery district (Fig. 1 does not show).The inorganic process liquid stream left through pipeline [d] joins extraction section [C], utilizes the almost pure toluene added through pipeline [h] to extract this inorganic process liquid stream there.Organic fluid containing the extraction of toluene, pimelinketone and cyclohexanone-oxime leaves extraction section [C] through pipeline [f], adds fresh pimelinketone through pipeline [e] in pipeline [f].The organic fluid of extraction is combined with fresh pimelinketone and is input to cyclohexanone-oxime through pipeline [b] and synthesizes district [B].Leave extraction section [C] through pipeline [g] after described inorganic process liquid stream extraction and be input to stripping zone [D].
Described in stripping zone [D], inorganic process liquid stream is by stripping, with after leave stripping zone [D] through pipeline [j].The aqueous fluid of primary aqueous, toluene and pimelinketone leaves stripping zone [D] through pipeline [i].Organic composition total content in the inorganic process liquid stream that pipeline [j] leaves generally lower than the inorganic process liquid stream inputted through pipeline [g] organic composition total content 1/10th.The inorganic process liquid stream left through pipeline [j] is input to charcoal absorption district [E], utilizes charcoal absorption removal part to remain machine composition there, then inorganic process liquid flows through pipeline [k] and leaves.
Optionally, only the inorganic process liquid stream partly left through pipeline [j] is input to charcoal absorption district and remainder is directly inputted to pipeline [k] or pipeline [k2] (Fig. 1 does not show).Optionally, the whole inorganic process liquid streams left through pipeline [j] are input in pipeline [k]; Namely this inorganic process liquid stream also need not through activated carbon treatment (Fig. 1 does not show).
Inorganic process liquid flow point in pipeline [k] is two portions and the fluid formed is carried further through pipeline [k1] and [k2].Described inorganic process liquid flows through pipeline [k1] and is transported to NOx uptake zone [F], and NOx gas is preferentially absorbed in inorganic process liquid stream there, thus ammonia is partially converted into nitrogen and/or original place forms nitric acid.Described NOx gas is input to NOx uptake zone [F] through pipeline [l].Leave the inorganic process liquid stream of NOx uptake zone [F] after being combined with the inorganic process liquid stream from pipeline [k2] through pipeline [m], be input to hydroxylammonium forming region [A] through pipeline [n].Optionally, can directly to the nitric acid (Fig. 1 does not show) inputting external source in inorganic process liquor body loop.
In hydroxylammonium synthesis district [A], in the aqueous solution containing phosphoric acid salt, nitrate and ammonia, with hydrogen selective reduction nitrate thus production hydroxylammonium under existing containing Pd heterogeneous catalyst.Hydrogen enters hydroxylammonium forming region [A] through input channel [o] and leaves through pipeline [p] from the tail gas of hydroxylammonium synthesis district [A] simultaneously.Inorganic process liquid containing phosphoric acid salt, nitrate, ammonia and azanol leaves hydroxylammonium synthesis district [A] through pipeline [a].
Describe the scheme of the continuation method removing molybdenum according to the present invention in fig. 2.The method of this removal molybdenum is a part for the commercial scale continuous method of being synthesized district and hydroxylammonium synthesis zone cyclic production oxime by inorganic process liquid at oxime.In oxime synthesis district, azanol and aldehydes or ketones react and generate oxime.In hydroxylammonium synthesis zone, under containing the existence of Pd and/or Pt catalyzer, generate azanol with the nitrate ion in hydrogen reduction organic process liquid or nitrogen oxide.Leaving molybdenum content in the inorganic process liquid of hydroxylammonium synthesis zone is in 0.3ppm (w/w) to 2ppm (w/w) scope.
Aqueous ammonia fluid is input to embedded mixing equipment [G] through pipeline [r].Inorganic process liquid containing molybdenum and iron flows through pipeline [s] and flows into embedded mixing equipment [G].The inorganic process liquid stream being input to embedded mixing equipment [G] is the 0.1wt% to 25wt% (Fig. 2 does not show) that oxime synthesizes in the inorganic process liquid of district and hydroxylammonium synthesis zone circulation.Optionally, the iron (Fig. 2 does not show) in embedded mixing equipment [G] forward direction inorganic process liquid fluid outside the amount of imports is joined at inorganic process liquid stream.By pipeline [t] to stopping the mixture flow that in container [H], the embedded mixing equipment of input [G] obtains.The mixture of aqueous ammonia and inorganic process liquid mean residence time in stop container [H] be 3 minutes within the scope of 200 minutes.Eliminating equipment [J] is inputed to through pipeline [u] by leaving stop container [H] ejecta containing ammonium ferric phosphate/molybdenum co-precipitation.From filtrate, remove ammonium ferric phosphate/molybdenum coprecipitate, this filtrate leaves eliminating equipment [J] through pipeline [v].Fluid containing ammonium ferric phosphate/molybdenum coprecipitate leaves described eliminating equipment [J] through pipeline [v].Fluid containing ammonium ferric phosphate/molybdenum coprecipitate leaves through pipeline [w] with batch mode or continuous print pattern.
Fig. 3 a schematically and partially describe basis
technology produces the continuous device of cyclohexanone-oxime, described in
technology removes the method for molybdenum containing with good grounds the present invention.[A], [B], [C], [D] and [F] district and pipeline [a] are to [j], and [l], [m], [o] and [p] such as Fig. 1 define.In pipeline [j], inorganic process liquid flow point is that the inorganic process liquid fluid that two portions are formed simultaneously is carried further through pipeline [j1] and [j2].The inorganic process liquid fluid carried through pipeline [j1] is a part for the inorganic process liquid of carrying through pipeline [j], and it is in 0.1wt% to 25wt% scope.Inorganic process liquid stream in pipeline [j] contains molybdenum and iron.The inorganic process liquid stream carried through pipeline [j1] is input to region [K].According to region of the present invention [K] containing the method removing molybdenum.The details of two different embodiments in region [K] as shown in figures 3 b and 3 c.
From inorganic process liquid diffluence except ammonium ferric phosphate/molybdenum coprecipitate, this inorganic process liquid flows through pipeline [x] and leaves region [K].Remove ammonium ferric phosphate/molybdenum coprecipitate from inorganic process liquid, join NOx uptake zone [F] through pipeline [x] this inorganic process liquid, NOx gas is absorbed there, and amino moiety is converted to nitrogen and/or original place formation nitric acid thus.The inorganic process liquid stream carried through pipeline [x] contains water, phosphoric acid salt, nitrate, ammonia, the molybdenum of reducing amount and the different organic compositions of optionally reducing amount.After the inorganic process liquid stream leaving NOx uptake zone [F] through pipeline [m] is combined with the inorganic process liquid stream from pipeline [j2], it joins hydroxylammonium synthesis district [A] through pipeline [n].Optionally, external source nitric acid can be directly inputted to inorganic process liquor body loop (Fig. 3 a does not show).
Optional, a part of inorganic process liquid is added into NOx uptake zone [F] (Fig. 3 a does not show) by pipeline [j2].
Optional, the inorganic process liquid that the co-precipitation of a part of ammonium ferric phosphate/molybdenum is endlessly removed walks around NOx uptake zone [F] (Fig. 3 a does not show) by pipeline [x].
Fig. 3 b schematically illustrates region in the present invention [K] and removes molybdenum embodiment, and it is basis
technology produces a part for the continuous device of cyclohexanone-oxime, described in
technology contains the method removing molybdenum.In this embodiment, region [K] be not containing charcoal absorption district.
The inorganic process liquid that stripping zone is discharged flows through pipeline [j1] and carries and pass through pump [L] and pump in pipeline [3].Inorganic process liquid in pipeline [3] is input to heat exchanger [M].Heat exchanger [M] can be any one heat exchanger.Preferably, heat exchanger [M] cools with refrigerant, such as water coolant or refrigerated water.Regulate inorganic process liquid to flow through pipeline [4] carry and be input in embedded mixing equipment [Q].Optionally, to the iron outside the amount of imports in the inorganic process liquid flowed through pipeline [j1] and/or [3] and/or [4].
Water is input to ammonia an adsorption device [N] through pipeline [6].Preferably, ammonia an adsorption device [N] is containing packed bed.Gaseous ammonia is input in an adsorption device [N] through pipeline [5].Aqueous ammonia flows through pipeline [7] and leaves an adsorption device [N] and enter pump [O].This pump [O] exports aqueous ammonia stream through pipeline [8].Aqueous ammonia in heat exchanger [P] input channel [8].Described heat exchanger [P] can be any one heat exchanger.Preferably, heat exchanger [P] cools with refrigerant, such as water coolant or refrigerated water.The inorganic process liquid after temperature is regulated to flow through pipeline [9] conveying.Aqueous ammonia in pipeline [9] is separated through pipeline [9a] and [9b].Aqueous ammonia stream in this pipeline [9b] is input to ammonia an adsorption device [N].
Aqueous ammonia is input to embedded mixing equipment [Q] through pipeline [9a].Preferably, in aqueous ammonia fluid, ammonia content is in 0.5 to 10wt% scope.The aqueous ammonia that optional area [K] is not input to embedded mixing equipment [Q] through pipeline [9a] containing an adsorption device [N], pump [O] and heat exchanger [P] simultaneously obtains (Fig. 3 b does not show) from other sources.
The mixture obtained in embedded mixing equipment [Q] leaves embedded mixing equipment [Q] and is input to through pipeline [10] and stops container [R].The mixture of aqueous ammonia and inorganic process liquid mean residence time in stop container [R] be 3 minutes within the scope of 200 minutes.Leave through pipeline [11] input in eliminating equipment [S] and stop container [R] ejecta containing ammonium ferric phosphate/molybdenum co-precipitation.Filtrate leaves eliminating equipment [S] through pipeline [x].The fluid containing ammonium ferric phosphate/molybdenum coprecipitate removed in eliminating equipment [S] leaves eliminating equipment [S] through pipeline [12].The fluid left containing ammonium ferric phosphate/molybdenum coprecipitate leaves with batch mode or continuous print pattern through pipeline [12].
Fig. 3 c schematically illustrates region in the present invention [K] and removes another embodiment of molybdenum, and it is basis
technology produces a part for the continuous device of cyclohexanone-oxime, described in
technology contains the method removing molybdenum.In this embodiment, region [K] is containing charcoal absorption district [E].
Region [L] is to [S], and pipeline [3] is to [12], and [x] definition as shown in Figure 3 b.
Optionally, the aqueous ammonia that district [K] is not input to embedded mixing equipment [Q] through pipeline [9a] containing an adsorption device [N], pump [O] and heat exchanger [P] simultaneously obtains (Fig. 3 c does not show) from other sources.
The inorganic process liquid fluid that stripping zone is discharged is carried through pipeline [j1] and joins gac district [E], remains machine composition there, and leave through pipeline [2] by charcoal absorption removal part.Inorganic process liquid in this pipeline [2] flows through pump [L] and pumps to pipeline [3].Optionally, only have part inorganic process liquid to flow through pump [L] in pipeline [2] and pump to pipeline [3] (Fig. 3 c does not show).
Optionally, extra iron is input in the inorganic process liquid flowed through pipeline [j1] and/or [2] and/or [3] and/or [4] (Fig. 3 c does not show).
Embodiment
The present invention is described by following examples and comparative example but is not limited to this.
Embodiment 1
In basis
technology year, cyclohexanone-oxime turnout was produce cyclohexanone-oxime in the continuous device of 200kta.The embodiment of the equipment same time domain [K] as described in Fig. 3 a adopted is as described in Fig. 3 b.
The molybdenum content that the inorganic process liquid leaving hydroxylammonium synthesis zone [A] has is approximately 1.6ppm (w/w).
The inorganic process liquid that about 1.2wt% stripping zone [D] exports is carried through pipeline [j1] and is passed through pump [L] and pumps to pipeline [3].In the inorganic process liquid that stripping zone [D] exports, concentration of iron is 140ppm (w/w).Inorganic process liquid stream in pipeline [3] is transported to heat exchanger [M], and described heat exchanger is plate and frame water cooler, and inorganic process liquid is cooled to about 14 DEG C from about 50 DEG C there.Described heat exchanger [M] adopts refrigerated water as refrigerant.The inorganic process liquid of cooling flows through pipeline [4] and carries and input embedded mixing equipment [Q].Extra iron is not added in the inorganic process liquid flowed in pipeline [j1] and/or [3] and/or [4].
Process water is through pipeline [6] input ammonia absorption equipment [N].Described ammonia absorption equipment [N] comprises the absorption tower that has packed bed.Gaseous ammonia is input to absorption equipment [N] through pipeline [5].Aqueous ammonia flows through pipeline [7] and leaves absorption equipment [N] and enter pump [O].Pump [O] exports aqueous ammonia fluid through pipeline [8].Aqueous ammonia in pipeline [8] flows into plate and frame heat exchanger [P].Heat exchanger [P] is the water cooler cooled as refrigerant with refrigerated water.The aqueous ammonia of cooling is carried through pipeline [9].The aqueous ammonia of pipeline [9] is separated by pipeline [9a] and [9b].By aqueous ammonia fluid input ammonia absorption equipment [N] in pipeline [9b].Input the aqueous ammonia of about 1.8t/hr through pipeline [9a] to embedded mixing equipment [Q], the temperature of this aqueous ammonia be 15 DEG C simultaneously containing the 3.6wt%NH that has an appointment
3.Embedded mixing equipment [Q] manages interior three-element spiral type static mixer by DN60.
The mixture that embedded mixing equipment [Q] obtains has pH value and is 4.6 and temperature is about 30 DEG C, and this mixture leaves embedded mixing equipment [Q] and is input to through pipeline [10] and stops in container [R].The mixture of aqueous ammonia and inorganic process liquid is 30 minutes at the mean residence time of stop container [R].Described stop container [R] has 3 nozzles: the inlet nozzle of upper vessel portion and the outlet nozzle of container lower end and water draining beak.Eliminating equipment [S] is input to by leaving the ejecta containing ammonium ferric phosphate/molybdenum coprecipitate stopping container [R].What eliminating equipment [S] adopted is
remove hydrogenation catalyst in technique and adopt Induction refining strainer.Filtrate leaves eliminating equipment [S] through pipeline [x].In eliminating equipment [S], remove ammonium ferric phosphate/molybdenum coprecipitate in batch, the fluid containing this ammonium ferric phosphate/molybdenum coprecipitate leaves eliminating equipment [S] through pipeline [12].
Inorganic process fluid is 1: 1.7 with the weight ratio of the aqueous ammonia adding embedded mixing equipment [Q].
The ammonium ferric phosphate removed in Induction refining strainer/molybdenum coprecipitate containing the 0.02wt%Mo that has an appointment with weighing scale after drying.
Be about 85.5% to producing the average selectivity of hydroxylammonium.
Comparative example 1
In basis
technology year, cyclohexanone-oxime turnout was produce cyclohexanone-oxime in the continuous device of 200kta.The equipment of the prior art adopted as described in Figure 1.
It is about 4ppm (w/w) that the inorganic process liquid leaving hydroxylammonium synthesis zone [A] during the production year has average molybdenum content.
Be about 82% to producing the average selectivity of hydroxylammonium.
Embodiment 1 clearly shows and Mo content in the inorganic process liquid leaving hydroxylammonium synthesis zone [A] can be maintained a lower level by removing Mo with the form of ammonium ferric phosphate/molybdenum coprecipitate.Given this about 3.5% can be improved to the selectivity of producing hydroxylammonium.
Claims (19)
1. one kind is passed through the commercial scale continuous method of producing oxime in oxime synthesis district and hydroxylammonium synthesis zone circulation inorganic process liquid, wherein leaving molybdenum content in the inorganic process liquid of hydroxylammonium synthesis zone is 0.3ppm (w/w) to 2ppm (w/w), and described method adopts:
I) by the equipment made containing molybdenum;
II) one can form the settling apparatus of ammonium ferric phosphate/molybdenum coprecipitate continuously;
III) one for removing the eliminating equipment of coprecipitate;
Wherein said method contains:
A. from circulation, get the inorganic process liquid of 0.1wt% to 25wt% circulation and it is combined with aqueous ammonia with the ejecta formed containing ammonium ferric phosphate/molybdenum coprecipitate in settling apparatus;
B. ejecta is inputed to eliminating equipment from settling apparatus;
C. in eliminating equipment, be separated described coprecipitate obtain filtrate, by the inorganic process liquid of this filtrate input circulation;
Wherein settling apparatus contains an embedded mixing equipment and a stop container.
2. method according to claim 1, the inorganic process liquid of wherein said inflow settling apparatus and the temperature of aqueous ammonia are all lower than 45 DEG C.
3. method according to claim 1, wherein said eliminating equipment is Induction refining strainer.
4. method according to claim 1, wherein the aqueous ammonia of discharging from embedded mixing equipment and inorganic process liquid mixture being introduced stops in container, wherein said aqueous ammonia and inorganic process liquid mixture the mean residence time stopping container be 1 minute within the scope of 900 minutes.
5. method according to claim 1, wherein said to add ammonia content in the aqueous ammonia of settling apparatus be in 0.5wt% to 10wt% scope.
6. method according to claim 1, in wherein said aqueous ammonia, ammonia content is in 1wt% to 5wt% scope.
7. method according to claim 1, it is in 3 to 6 scopes that the industrial process liquids of wherein said acquisition and aqueous ammonia mixture have pH value.
8. method according to claim 1, the wherein said aqueous ammonia adding settling apparatus obtains by dissolving gaseous ammonia in water.
9. method according to claim 1, the wherein said aqueous ammonia refrigerated water adding settling apparatus cools.
10. method according to claim 1, wherein said inorganic process liquid used activated carbon treatment before being input to settling apparatus.
11. methods according to claim 1, wherein said inorganic process liquid used steam stripped before being input to settling apparatus.
12. methods according to claim 1, wherein said inorganic process liquid extracted with toluene before being input to settling apparatus.
13. methods according to claim 1, wherein join the filtrate that eliminating equipment flows out in steam stripped tower to remove water vapor.
14. methods according to claim 1, are wherein input to the filtrate that eliminating equipment flows out in NOx absorption equipment.
15. methods according to claim 1, are wherein arranged in filtrate being input to that eliminating equipment flows out in the tank after NOx absorption equipment.
16. methods according to claim 1, wherein said oxime is cyclohexanone-oxime, cyclobutanone oxime or cyclododecanone oxime.
17. methods according to claim 1, wherein add containing molysite in the inorganic process liquid being injected towards settling apparatus.
18. methods according to claim 1, wherein said embedded mixing equipment is static mixer.
19. methods according to claim 1, wherein inorganic process liquid is in 1: 0.4 to 1: 4 scopes with the weight ratio joining the aqueous ammonia in precipitation apparatus.
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