CN103357217A - Method for cleaning filter used in continuous production of hydroxylammonium - Google Patents
Method for cleaning filter used in continuous production of hydroxylammonium Download PDFInfo
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- CN103357217A CN103357217A CN2013101091639A CN201310109163A CN103357217A CN 103357217 A CN103357217 A CN 103357217A CN 2013101091639 A CN2013101091639 A CN 2013101091639A CN 201310109163 A CN201310109163 A CN 201310109163A CN 103357217 A CN103357217 A CN 103357217A
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- hydroxylammonium
- filter candle
- candle
- filter
- prepare
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Abstract
The invention relates to a method for producing hydroxylammonium by a continuous process. The method comprises a filtering method for recovering solid catalyst particles by utilizing a filter candle, wherein the method for cleaning the filter candle at least comprises the following steps of: i) enabling the filter candle to be in contact with an alkaline solution with the concentration of 0.2-4mol/l at the temperature of 40-110 DEG C; ii) then performing treatment on the filter candle for at least 30s by using ultrasonic waves with the power of at least 10w/l; iii) cleaning the filter candle before re-placing the filter candle in a filtering region; and iv) recovering the solid catalyst particles from wastewater obtained in the steps i), ii) or iii), and recovering metals from the recovered catalyst particles.
Description
Technical field
The present invention relates to a kind of continuation method of producing hydroxylammonium, the method comprises the filter method that utilizes the filter element that contained filter candle to reclaim solid catalyst particle from moisture inorganic process liquid, and wherein cleaning the described method of crossing filter candle is to carry out first carrying out the ultrasonic wave processing after the alkali treatment.
Technical background
The important use of hydroxyl ammonium salt is for preparing oxime from ketone or aldehyde, particularly preparing cyclohexanone oxime by cyclohexanone.With regard to the preparation of this oxime, in known round-robin method, moisture acidic buffer reaction medium keeps circulation in the synthetic district of hydroxyl ammonium salt and the synthetic district of oxime.The buffer salt that reaction medium is derived by for example phosphoric acid and/or sulfuric acid and these acid, for example basic salt and/or ammonium salt acidic buffer.In the synthetic district of hydroxyl ammonium salt, with hydrogen the nitrate ion in the circulation inorganic liquid or nitrogen oxide are transformed into azanol.
Azanol forms corresponding hydroxyl ammonium salt with free buffering acid reaction, and with this synthetic district of hydroxyl ammonium salt input oxime, it generates corresponding oxime with reactive ketone there, discharges simultaneously sour subsequently.From reaction medium, isolate after the oxime, reaction medium is recycled to the synthetic district of hydroxyl ammonium salt and adds new nitrate ion or nitrogen oxide in reaction medium.
In the situation that synthesize hydroxyl ammonium salt with phosphoric acid and nitrate solution, above-mentioned chemistry side should be expressed as follows:
Reaction 1) at the synthetic district's preparation of hydroxyl ammonium salt hydroxylammonium;
2H
3PO
4+NO
3 -+3H
2-→NH
3OH
++2H
2PO
4 -+2H
2O
First reaction is heterogeneous catalysis.Preferably, catalyst exists as the decentralized photo in the liquid reaction mixture with the form of homodisperse solid.
The mixture of reaction products of the first step is the moisture inorganic process liquid that contains the solid catalyst particle suspended substance in hydroxylammonium salt solution.
By course of reaction as can be known, inorganic process liquid can contain the intermediate material of azanol for example or ammonia, and it also can be turned to for example hydroxylammonium or ammonium by proton.That is to say, azanol and hydroxylammonium can be interpreted as azanol and/or hydroxylammonium according to the present invention, and ammonia or ammonium can be understood as ammonia and/or ammonium simultaneously.
Before should moisture inorganic process liquid being input to the synthetic district of oxime, preferably from this moisture inorganic process liquid, isolate solid catalyst particle.After the filtration, this inorganic process liquid is hydroxylammonium salt solution filtrate.
Above-mentioned method comprises DSM's
Method (with reference to e.g.H.J.Damme, J.T.van Goolen and A.H.de Rooij, Cyclohexanone oxime made without by-product (NH
4)
2SO
4, July 10,1972, Chemical Engineering; Pp 54/55 or Ullmann ' s Encyclopedia of Industrial Chemistry (2005) at page6/7under chapter Caprolactam.
Although the in decades preparation of hydroxylammonium is known and to improve this known preparation method also for many years studied, the existing commercial run that generally has continuation is Shortcomings still.
Concrete is that in known continuous process, the recycling of crossing filter candle is a difficult problem.
WO01/46070 has described a kind of utilization by the method for cake filtration separation of hydroxylammonium salt solution from the aqueous reaction mixture that contains solid catalyst particle of asymmetric filter.
EP577213 has described a kind of method of utilizing cross-flow filtration technology purifying hydroxylammonium salt solution from the aqueous reaction mixture that contains solid catalyst particle.
US4081516 has described a kind of method of purifying hydroxylammonium salt solution, wherein adds starch, gelatin, thus polyacrylamide or polyvinyl alcohol reduce filtration resistance as flocculant.
WO03/080221 has described a kind of conventional filtration device assembly of separation of the fluid from solid particle and substantially discloses and can remove legal phase filter rinsed with ultrasonic wave or subsonic speed.
US7799144 discloses a kind of cleaning method of the filter element for the filtering molten polymer, this filter element polymer blocking that is cured at least in part.The method comprises uses superheated steam, pyrolysis, oxidation, Ultrasonic Cleaning, alkali acid treatment.
This shows, rely on the traditional like this cleaning method of for example backwash, can not produce continuously the mistake filter candle of the costliness of using in the hydroxylammonium process by effective cleaning, finally usually is that the mistake filter candle is eliminated and thrown aside.
As everyone knows, for improving reusability, can adopt for example ultrasonic wave, alkali or acid treatment serial of methods cleaning and filtering hole.
Yet, too much contact the filter capacity that alkali, acid or ultrasonic wave can reduce filter, therefore need between the cleaning of the best and reusability, to keep balance.
The regeneration of hydroxylamine catalyst filter metal agglomeration filter core, Guan Jian, Ba Ling company of Sinopec Group, Yueyang 414007;＜chemical industry progress 〉, the 22nd volume in 2003; A kind of renovation process of hydroxylamine catalyst filter element is disclosed.This article has adopted a kind of comprehensive method regeneration filter core.Successively filter core is immersed in NaOH solution after filter is removed, the sharp baking of ultrasonic cleaning is processed.How from the waste water that regenerative process is discharged, not reclaim catalyst but this article is open.
Therefore, the purpose of this invention is to provide a kind of cleaning uses cross filter candle and reclaim improving one's methods of catalyst granules in producing the hydroxylammonium process.
Summary of the invention
The invention provides a kind of method with the continuous process production hydroxylammonium, the method comprises the filter method that utilizes the filtering area that contained filter candle to reclaim solid catalyst particle from the moisture inorganic process liquid that is applied in hydroxylammonium production, wherein cleans the described method of crossing filter candle and may further comprise the steps at least:
I) will cross filter candle and concentration is that the aqueous slkali of 0.2-4mol/l contacts under temperature 40-110 ℃;
Ii) then processed filter candle at least 30 seconds with the ultrasonic wave of at least 10 watts/liters of power; With
Iii) before again will crossing filter candle and placing filtering area, the washing and filtering candle;
Iv) from step I), ii) or iii) in reclaim solid catalyst particle in the waste water that obtains.
Found that, before processing with ultrasonic wave, can remove better catalyst granules with the aqueous slkali processing.Further, the ultrasonic wave in later stage is processed and to be helped to remove any sticking together at the aqueous slkali of crossing on the filter candle, is undesirable because introduce alkali in the hydroxylammonium production when having served as filter candle and turning back to filtering area.In addition, the heavy metal in the catalyst granules that reclaims in the cleaning process can be recovered.
Method of the present invention can effectively be removed solid catalyst particle and be crossed simultaneously filter candle and can be reused.Utilize said method can reduce production costs and can be recycled to more catalyst.
Preferably, catalyst is included in liquid, aqueous middle hydrogenation nitric acid, the heterogeneous catalysis of nitrate or nitrogen oxide.Preferably, at liquid, aqueous middle hydrogenation nitric acid, the described catalyst of nitrate or nitrogen oxide is made of the heavy metal that is positioned on the carrier carbon.
The catalyst that uses in the hydroxyl ammonium salt in preparation mainly is comprised of the metal that is selected from platinum family, such as be positioned on the carbon carrier for example with palladium or (palladium+platinum) catalyst as active component.Can activate this catalyst by there being one or more catalyst activators.Catalyst activator can be to be selected from copper, silver, cadmium, mercury, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony and bismuth.Most preferably, this catalyst activator is germanium.
The preferential composition that uses catalyst and catalytic activity agent, example comprises GeO
2/ Pd composition.
Preferably, the content of this catalyst activator is 0.01-100mg/g catalyst (being positioned at the active component of carrier mass), preferably 0.05-50mg/g catalyst, more preferably 0.1-10mg/g catalyst, most preferably 1-7mg/g catalyst.
The compound that contains described element, for example oxide, nitrate, phosphate, sulfate, halide and acetate also can be used as catalyst activator.Element described in US3767758 or their compound, can be directly as catalyst or be added in the reaction medium.
The catalyst that (reaction 1) used in the preparation hydroxylammonium salt solution preferably contains and is positioned at heavy metal on the carrier, is preferably placed at the platinum (Pt) on the carrier, palladium (Pd) or platinum and palladium composition.
Although usually tend to use pure palladium, pure palladium may contain certain platinum impurity, palladium in the pure palladium: the part by weight of platinum can be different.Preferably, palladium contains the platinum that is lower than 25wt%, more preferably less than 5wt%, further preferably is lower than 2wt%, particularly preferably is lower than the platinum of 1wt%.
Preferably, carrier comprises carbon (for example graphite, carbon black, perhaps activated carbon) or alumina support, more preferably graphite or activated carbon.The catalyst that uses in the synthetic district of hydroxyl ammonium salt preferably contains the heavy metal of 1-25wt%, and the more preferably heavy metal of 5-15wt% is with respect to the gross weight of carrier and catalyst.
As a rule, the consumption of the catalyst in the synthetic district of hydroxyl ammonium salt is 0.05-25wt%, is preferably 0.2-15wt%, and 0.5-5wt% more preferably is with respect to the inorganic process liquid gross weight in the synthetic district of hydroxyl ammonium salt.
The particle mean size of catalyst granules is generally 1-150 μ m, preferred 2-100 μ m, more preferably 3-60 μ m, most preferably 5-40 μ m.So-called " particle mean size " refers to the particle of 50vol% greater than nominal diameter.
The inventive method helps to clean well known in the art such as filter elements such as symmetrical and asymmetric excessively filter candles.
In the preferred embodiments of the present invention, the method for cleaning and filtering candle contains following steps at least:
I) remove filter element from filtering area;
II) removed filter candle from filter element;
III) will cross filter candle and concentration is that the aqueous slkali of 0.2-4mol/l contacts;
IV) add hot alkaline solution to 40-110 ℃;
V) from aqueous slkali, removed filter candle;
VI) will cross filter candle and place ultrasonic container;
VII) add water and water is heated to 40-110 ℃ to crossing filter candle;
VIII) processed filter candle at least 30 seconds with the ultrasonic wave of at least 10 watts/liters of power;
IX) ultrasonic container is carried out draining;
X) repeating step VII), step VIII) and step IX) more than at least twice;
XI) before again will crossing filter candle and placing filtering area, the washing and filtering candle;
XII) in waste water, reclaim solid catalyst particle.
Preferably, before filter element is removed from filtering area, carry out backwash from cross filter candle, to remove catalyst as much as possible.This can make, and remover is more efficient more easily to be reclaimed with catalyst.Filtering area can be a filtering container.
After removing filter candle from filter element, often discharged as far as possible wherein inorganic process liquid by being inverted filter candle.Then will cross filter candle and contact with aqueous slkali, preferably be immersed in the buck bath.
Preferred bases solution is NaOH, KOH and/or LiOH.Usually select NaOH.
The preferred bases solution concentration is 0.75-2mol/l, more preferably 1-1.75mol/l.
Preferably, add hot alkaline solution to 50-90 ℃, especially 50-60 ℃.Preferably, adopt low-pressure steam to add hot alkaline solution.Preferably, will cross filter candle and contact 1-72 hour with aqueous slkali, more preferably 2-48 hour, especially 5-36 hour.
After from aqueous slkali, removing filter candle, often by being inverted filter candle it was carried out draining.
Then in ultrasonic cleaning container, add water, preferably, add deionized water and preferably, be placed in the container to cross the mode that filter candle is given a shock equally.In specific embodiments of the invention, ultrasonic cleaning container comprises 8 supersonic generators and 2 generators and can hold 8 and cross filter candles.
Preferably, use by the water in the low-pressure steam heating ultrasonic cleaning container.
Preferably, be at least 15 watts/liter ultrasonic wave with power and processed filter candle.
Preferably, processed filter candle at least 5 minutes with ultrasonic wave, more preferably at least 10 minutes.
Preferably, process at least twice with ultrasonic wave to crossing filter candle.
Can reclaim by the method for knowing the catalyst in the waste water.
For last cleaning step, preferably the emptying filter candle of crossing is fixed on the interior flushing line of flushing frame.Preferably with the flushing of low-pressure steam and water wheels stream, more preferably with deionized water rinsing at least 3 times, each 30 seconds.Preferably will cross filter candle washes from the inside to surface.
At step XI) in cross after the filter candle flushing finishes, preferably be dried.Preferably, use low-pressure steam drying at least 20 minutes.
Before will crossing filter candle and again placing filtering area, checked whether filter candle has the crack and measure pressure reduction with differential pressure indicator.Preferred air velocity flows through the purification filtering candle when being 0.4 liter/second air pressure difference is less than 7000 handkerchiefs/(crossing filter candle length).
In fact, if when air velocity is 0.4 liter/second, the pressure drop on the polishing filter is equal to or greater than 7000 handkerchiefs/(cross filter candle length), so will the repeated washing flow process or will cross filter candle and eliminate.
The production equipment of preparation hydroxylammonium can be any suitable reactor, for example has the reactor of mechanical agitator or has the reactor of operation post, more preferably bubble column.NL6908934 has described the example of suitable bubble column.The typical reactor configuration that can prepare moisture hydroxylammonium salt solution and energy solid catalyst particle is the hydrogenation bubble-column reactor with cooling section.Reactor configurations usually comprises a lot of groups gas Disengagement zone and filtering area.
Embodiment
By the gas separator tube hydroxylammonium salt solution is transferred to the screen pipe that contains the filter element that is useful on filtration step from bubble-column reactor.Filter element comprises one group of filter candle of crossing that is used for filtration.Partly (usually about general 3-10%) hydroxylammonium salt solution filtrate is transferred to the filtrate pipe from screen pipe, transfers to from filtrate pipe afterwards and transfer to the synthetic district of oxime the filtrate separator tube again from the filtrate separator tube.
The inorganic process liquid that contains hydroxylammonium salt solution by filtration significantly discharges catalyst granules.The average grain diameter of catalyst granules (10wt% palladium/carbon) is 15 μ m.
The filter candle of crossing that uses is:
1. non-ly property is crossed filter candle (Krebsoge, model Sika-R3AS) it has the filter course aperture of 3 μ m, the filtration bed thickness (example I) of total wall thickness of 2.2mm and 200mm for one kind;
2. a routine crosses filter candle (Krebsoge, model Sika-R3IS) it has the aperture of 3 μ m and the wall thickness of 2.2mm (example II);
The method of crossing filter candle of cleaning among embodiment 1 and the embodiment 2 comprises the steps:
I) remove filter element from filtering area;
II) removed filter candle from filter element;
III) will cross filter candle and concentration is that the NaOH solution of 1.25mol/l contacts;
IV) adopt low-pressure steam to add hot alkaline solution to approximately 60 ℃;
V) from aqueous slkali, removed filter candle after 24 hours;
VI) will cross filter candle and place ultrasonic container;
VII) add water and adopt low-pressure steam that water is heated to about 100 ℃ to crossing filter candle;
VIII) processed filter candle 30 minutes with the ultrasonic wave of 18 watts/liter of power;
IX) emptying ultrasonic container;
X) repeating step VII), step VIII) and step IX) twice;
XI) cleaning and filtering candle;
XII) employing low-pressure steam dry filter is lit up and is measured pressure reduction with differential pressure indicator and detect whether the crack is arranged
XIII) in waste water, reclaim solid catalyst particle.
In above-mentioned two examples, when air velocity is 0.4 liter/second, flow through the air pressure difference of purification filtering candle less than 7000 handkerchiefs/(crossing filter candle length).In addition, filter does not have any crack.Two filters all can be utilized to filter hydroxylammonium salt solution again.From the palladium/carbon that contains catalyst granules that reclaims, reclaim palladium.
Claims (9)
1. method with the continuous process production hydroxylammonium, the method comprises the filter method that utilizes the filtering area that contained filter candle to reclaim solid catalyst particle from the moisture inorganic process liquid that is applied in hydroxylammonium production, wherein cleans the described method of crossing filter candle and may further comprise the steps at least:
I) will cross filter candle and concentration is that the aqueous slkali of 0.2-4mol/l contacts under temperature 40-110 ℃;
Ii) then processed filter candle at least 30 seconds with the ultrasonic wave of at least 10 watts/liters of power; With
Iii) before again will crossing filter candle and placing filtering area, the cleaning and filtering candle;
Iv) from step I), ii) or iii) in reclaim solid catalyst particle in the waste water that obtains.
2. the method for preparing according to claim 1 hydroxylammonium, wherein step I) in aqueous slkali comprise NaOH.
3. prepare the method for hydroxylammonium, wherein step I according to any one of the claims) in cross filter candle and contact 1-72 hour with aqueous slkali.
4. prepare the method for hydroxylammonium according to any one of the claims, wherein repeating step ii) at least twice.
5. prepare the method for hydroxylammonium according to any one of the claims, wherein repeating step iii) at least twice.
6. prepare the method for hydroxylammonium according to any one of the claims, wherein step I i) in low-pressure steam and water wheels stream washing and filtering candle.
7. prepare the method for hydroxylammonium according to any one of the claims, wherein step I ii) finish after with low-pressure steam dry filter candle.
8. prepare the method for hydroxylammonium according to any one of the claims, the air pressure difference that flows through the purification filtering candle when wherein air velocity is 0.4 liter/second is for less than 7000 handkerchiefs/(crossing filter candle length).
9. prepare the method for hydroxylammonium according to any one of the claims, wherein solid catalyst particle has average grain diameter position 5-40 μ m usually.
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|---|---|---|---|
| CN2013101091639A CN103357217A (en) | 2012-03-31 | 2013-03-29 | Method for cleaning filter used in continuous production of hydroxylammonium |
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| CN201210101324 | 2012-03-31 | ||
| CN201210101324.5 | 2012-03-31 | ||
| CN2013101091639A CN103357217A (en) | 2012-03-31 | 2013-03-29 | Method for cleaning filter used in continuous production of hydroxylammonium |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117245A (en) * | 2014-07-31 | 2014-10-29 | 新乡市胜达过滤净化技术有限公司 | Method for cleaning metal powder sintered filter element |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084136A (en) * | 1992-07-02 | 1994-03-23 | Dsm有限公司 | The preparation of hydroxylammonium salt solution and purification process |
| CN1248479A (en) * | 1998-09-22 | 2000-03-29 | 巴陵石油化工公司鹰山石油化工厂 | Regeneration method for metal powder sintered filter element |
| CN1273879A (en) * | 1999-05-15 | 2000-11-22 | 樊哲华 | Process for regenerating noble metal catalyst for synthesizing hydroxyamine salt |
| JP2010064015A (en) * | 2008-09-11 | 2010-03-25 | Chuden Plant Co Ltd | Filter element cleaning apparatus |
-
2013
- 2013-03-29 CN CN2013101091639A patent/CN103357217A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084136A (en) * | 1992-07-02 | 1994-03-23 | Dsm有限公司 | The preparation of hydroxylammonium salt solution and purification process |
| CN1248479A (en) * | 1998-09-22 | 2000-03-29 | 巴陵石油化工公司鹰山石油化工厂 | Regeneration method for metal powder sintered filter element |
| CN1273879A (en) * | 1999-05-15 | 2000-11-22 | 樊哲华 | Process for regenerating noble metal catalyst for synthesizing hydroxyamine salt |
| JP2010064015A (en) * | 2008-09-11 | 2010-03-25 | Chuden Plant Co Ltd | Filter element cleaning apparatus |
Non-Patent Citations (2)
| Title |
|---|
| 崔觉剑等: "液相催化加氢中催化剂的分离方法", 《化工生产与技术》 * |
| 管健: "羟胺催化剂过滤器金属烧结滤芯的再生", 《化工进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117245A (en) * | 2014-07-31 | 2014-10-29 | 新乡市胜达过滤净化技术有限公司 | Method for cleaning metal powder sintered filter element |
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Application publication date: 20131023 |