CN1421383A - Amorphous skeletal-nickel hydrogenating catalyst for anthraquinone process of preparing hydrogen peroxide and its prepn - Google Patents
Amorphous skeletal-nickel hydrogenating catalyst for anthraquinone process of preparing hydrogen peroxide and its prepn Download PDFInfo
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- CN1421383A CN1421383A CN 02150722 CN02150722A CN1421383A CN 1421383 A CN1421383 A CN 1421383A CN 02150722 CN02150722 CN 02150722 CN 02150722 A CN02150722 A CN 02150722A CN 1421383 A CN1421383 A CN 1421383A
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Abstract
The present invention belongs to the field of chemical technology and is especially one catalyst for anthraquinone hydrogenation process of preparing hydrogen peroxide and its preparation. The catalyst is obtained with some alloy and through active treatment with alkali solution and the alloy consists of Ni, Al and metal additive including one or several of Cr, Mo, W, Fe, Co, Cu and Zn. The catalyst is one kind of amorphous skeleton alloy catalyst prepared through high temperature melting of metal components, quenching stress to obtain alloy strip or scaly alloy, grinding, sieving and activation in alkali solution. Compared with traditional Raney Ni catalyst, the said catalyst has high anthraquinone hydrogenation activity and high selectivity.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to be used for new catalyst of anthraquinone hydrogenation and preparation method thereof in a kind of technology by anthraquinone preparation hydrogen peroxide.
Background technology
Hydrogen peroxide is a kind of very important Chemicals, uses very extensive.In textile and dyeing industry, with hydrogen peroxide fabric is bleached destarch, because it is little to the fibre strength loss, treated fabric is difficult for brightness reversion, good hand feeling.Hydrogen peroxide can be used for association with pulp bleaching in paper industry and deinking is handled.In electronic industry, frequent and other material wiring solution-formings of hydrogen peroxide are as etching reagent and clean-out system.Hydrogen peroxide can be used for sterilizing agent, milk and milk preparation sterilization, the bread fermentation of sterilization, the canning factory of soft packaging paper, decolouring of food fibres etc. in foodstuffs industry.Hydrogen peroxide also has sterilization, and 3% hydrogen peroxide dilute solution is used as sterilant in hospital.Same owing to hydrogen peroxide non-secondary pollution deposits yields in sterilization and disinfection, its application in environmental improvement also receives very big concern.Especially in the improvement of waste water, use hydrogen peroxide can reduce the harmful secondary pollutants such as a large amount of haloforms that use chlorine to bring as disinfection sanitizer.Because hydrogen peroxide is a reductive agent, be again oxygenant, so it also has sizable application aspect chemical industry.Hydrogen peroxide is used for extensively producing epoxide, organo-peroxide and inorganic peroxy acid and salt thereof.
Plurality of advantages such as the method for preparing hydrogen peroxide mainly contains isopropanol oxidation method, electrolytic process and anthraquinone, and a kind of method in back has that the automatization of being easy to, throughput are big, cost and energy consumption are low have become the first-selection in the hydrogen peroxide preparation.The technology of anthraquinone preparation hydrogen peroxide mainly is made up of following several steps: at first the anthraquinone of certain form is dissolved in the specific solvent and forms working fluid, be dissolved in anthraquinone in the solvent and hydrogenation reaction takes place in the presence of hydrogenation catalyst obtain hydrofenating anthraquinone; Feed oxygen-containing gas in the working fluid after hydrogenation and obtain hydrogen peroxide, hydrofenating anthraquinone changes back to anthraquinone again simultaneously; The hydrogen peroxide that generates is purified through extraction, concentrates and gets final product finished product; Working fluid then process recycles after regenerating, dewater and purifying.Anthraquinone hydrogenation catalyst difference according to use can be divided into nickel catalyzator method and palladium catalyst method again, using skeleton nickel once was the main flow of anthraquinone preparation hydrogen peroxide as catalyzer, but use traditional skeleton nickel to be catalyzer, the selectivity of anthraquinone hydrogenation is relatively poor, thereby the unnecessary consumption that has caused a large amount of anthraquinones and hydrogen, the cost of increase hydrogen peroxide; Therefore in operating process for more anthraquinone is consumed, general technology is controlled at the hydrogenation of anthraquinone below 70%, but this has directly had influence on the production efficiency of hydrogen peroxide again.Palladium catalyst then shows good selectivity in anthraquinone hydrogenation.Yet, owing to the cost an arm and a leg production cost of the hydrogen peroxide that makes that this method makes of palladium catalyst is higher.
Summary of the invention
The objective of the invention is to propose a kind of catalytic efficiency height, good reaction selectivity, in anthraquinone preparation hydrogen peroxide process, be used for the new amorphous state skeleton catayst of anthraquinone shortening, and proposed this Preparation of catalysts method.
The catalyzer that is used for anthraquinone hydrogenation in the anthraquinone preparation hydrogen peroxide process provided by the invention is a kind of nickeliferous amorphous raney catalyzer, and its preparation is made up of following steps:
(5) nickel, aluminium and metal additive M are heated to molten state;
(6) prepare frangible alloy strip or flakey alloy with liquid sudden cold single-roller method;
(7) grind the screening alloy;
(8) in basic solution, after handling, activity obtains the amorphous raney catalyzer.
Alloy is made up of nickel, aluminium and metal additive M, and wherein nickel accounts for 20～60wt%, and M accounts for 0.1～10wt%, and all the other are aluminium.Main component is Ni in the alloy
2Al
3And NiAl
3With metal simple-substance mixture high-temperature fusion in inert atmosphere, and under protection of inert gas, prepare alloy strip and scale through the roll shaft of rotation, the rotating speed of roll shaft 〉=500 rev/min; The alloy that makes filters out 8～200 purpose particles through grinding; The alloying pellet that filters out is in 30 ℃ to 120 ℃ temperature range; preferred 70 ℃ to 100 ℃; under protection of inert gas alloying pellet joined among the NaOH or the KOH aqueous solution in the stirring, the concentration of described basic solution is 5～50wt%, preferred 10～40wt%.
The skeleton catalyst for hydrogenation that is made by above-mentioned steps provided by the invention is made up of nickel, aluminium and metal additive M, and wherein nickel accounts for 50～90wt%, and aluminium accounts for 10～40wt%, and M accounts for 0.1～10wt%, and total amount is 100%.
Metal additive M of the present invention can form in the metallic element of sosoloid one or more with nickel and aluminium, in the preferred elements periodictable in IB family, IIB family, group vib, the group VIII metallic element one or more, in more preferred IB family, group vib, the group VIII metallic element one or more, metal additive commonly used are one or more among Cr, Mo, W, Fe, Cu, Co, the Zn.
According to catalyzer provided by the invention, active constituent nickel exists with the non-crystalline state form except that existing with the alumel form on a small quantity mostly, and metal additive M and nickel form alloy or exists with oxide form separately.At this moment, except that smaller alumel peak occurring, ° located a broad diffraction peak (as shown in Figure 1) on the X-ray diffractogram of measuring with CuK α target, be the characteristic diffraction peak of ni based amorphous alloy in 2 θ=45.Activity of such catalysts provided by the invention can be tested with the following method:
Intermittently investigate catalyst activity in the tank reactor at the 0.22L stainless steel.Anthraquinone is dissolved in the solvent, and put into still with catalyzer, anthraquinone adopts 2-ethyl-anthraquinone or 2-amyl anthraquinone, solvent can be that the mixed solution of heavy aromatics and trioctyl phosphate also can be the mixed solution of heavy aromatics and terpene pine camphor, wherein the shared volume ratio of heavy aromatics is 40～80%, and the concentration of anthraquinone is 30～110g/L.Autoclave sealing back is with hydrogen exchange three times, to remove the air in the still.Preliminary filling hydrogen post-heating begins reaction to temperature of reaction, and temperature of reaction is 30～100 ℃, preferred 40～70 ℃; Reaction pressure is 1～10atm, more excellent 1～3atm.Stir speed (S.S.) is greater than 1000 rev/mins during reaction.The sampling of reaction process discontinuous feeds oxygen-containing gas after the adding small amounts of phosphoric acid in the sample that takes out, can be pure oxygen, can be air also, after for some time, and the hydrogen peroxide that the water extraction generates, hydrogen peroxide content adopts the potassium permanganate process titration.Reaction back working fluid adopts efficient liquid phase chromatographic analysis wherein to form.
The present invention has property and the undersaturated active sites of coordination such as a large amount of chemistry by the amorphous raney catalyzer that sudden cooling method makes owing to the surface, and catalyzed reaction is had high reactivity and highly selective, is expected to replace traditional skeletal nickel catalyst and palladium catalyst.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of catalyzer.
Fig. 2 is a yield situation of using the hydrogen peroxide of catalyzer of the present invention in the anthraquinone preparation hydrogen peroxide process.
Embodiment
Further describe the present invention below by specific embodiment.Embodiment 1: the preparation of skeleton nickel aluminium ferrochrome amorphous catalyst
Alloy formula pure nickel 900g
Fine aluminium 800g
Pure iron 100g
Pure chromium 200g
Alloy powder preparation: with nickel, aluminium, chromium, iron pack into ultrasonic gas atomization equipment and process furnace internal heating; with nitrogen is protection gas; the melting injection temperature is 1400 ± 20 ℃, and roll shaft speed is 800 rev/mins, makes the sheet alloy and obtains 100～200 purpose particles through grinding.
Catalyst activation: the above-mentioned alloy that obtains joined in 20% the sodium hydroxide solution, elevated temperature to 90 ℃ is at N
2Protective atmosphere stirred 2 hours down, and the cooling back is washed till neutrality with deionized water, removed water in the catalyzer with dehydrated alcohol again.The part characterization result of catalyzer is shown in table one.
Body phase composite and specific surface area before and after table one, the activation of NiAlCrFe alloy
Sample body phase composite (atomic ratio) specific surface area (m
2.g
-1) specific activity surface (m
2.g
-1)
Alloy Ni
30.3Al
58.6Cr
7.5Fe
3.60.021 1
Catalyst n i
74.3Al
23.2Cr
1.6Fe
0.9111.2 27.3
Anthraquinone hydrogenation: the 3.5g anthraquinone is dissolved in the solvent that 70mL was made into by heavy aromatics and trioctyl phosphate in 7: 3 by volume, and put in the reactor in the lump with the 0.5g catalyzer, charge into hydrogen pressure to 3atm, temperature of reaction is controlled at 50 ± 2 ℃, 1000 rev/mins of stir speed (S.S.)s.Gained the results are shown in Figure 2: the yield of hydrogen peroxide can be near 100%, far surpasses 70% level of conventional skeleton nickel.Embodiment 2: the preparation of skeleton nickel-aluminum-molybdenum amorphous catalyst
With the pure nickel of appropriate amount, pure molybdenum and fine aluminium pack into ultrasonic gas atomization equipment and process furnace internal heating; with nitrogen is protection gas, and the melting injection temperature is 1400 ± 20 ℃, and roll shaft speed is 800 rev/mins; make the sheet alloy of different molybdenum content, obtain 100～200 purpose particles through grinding.Alloy makes catalyzer after the activation through 20% sodium hydroxide solution down in 90 ℃, 0.5g catalyzer and the 3.5g anthraquinone that is dissolved in the solvent that 70mL was made into by heavy aromatics and trioctyl phosphate in 7: 3 are by volume put in the reactor, be used for anthraquinone hydrogenation, it the results are shown in table two.
Body phase composite and hydrogenation activity before and after the NiMoAl alloy activation of table two, different Mo content
Alloy catalyst initial rate H
2O
2Yield H
4The amount of eAQ
*
(atom?ratio) (atom?ratio) (mmol/min) (％) (％)
Ni
31.77Al
68.23 Ni
78.53Al
21.47 0.41 90 29.1
Ni
30.55Al
68.82Mo
0.83 Ni
79.25Al
20.20Mo
0.55 0.47 100 20.3
Ni
30.38Al
68.67M0
0.95 Ni
80.80Al
18.51Mo
0.69 0.52 100 21.2
Ni
28.97Al
69.12Mo
1.91 Ni
82.40Al
16.42Mo
1.18 0.89 100 32.9
Ni
26.10Al
70.04Mo
3.86 Ni
87.04Al
10.47Mo
2.49 0.55 100 14.9
Claims (5)
1, the skeletal nickel catalyst that is used for anthraquinone hydrogenation in a kind of anthraquinone preparation hydrogen peroxide process, it is characterized in that the each component ratio is: nickel accounts for 50～90wt%, aluminium accounts for 10～40wt%, M accounts for 0.1～10wt%, total amount is 100%, and M can form in the metallic element of sosoloid one or more with nickel and aluminium.
2, skeletal nickel catalyst according to claim 1 is characterized in that metal additive M is one or more among Cr, Mo, W, Fe, Co, Cu, the Zn.
3, skeletal nickel catalyst according to claim 1 and 2 is characterized in that nickel mainly exists with the form of elemental nickel and alumel, and aluminium and M exist with alloy or oxide form.
4, a kind of Preparation of catalysts method as claimed in claim 1 is characterized in that concrete steps are:
(1) nickel, aluminium and metal additive M are heated to molten state;
(2) prepare frangible alloy strip or flakey alloy with liquid sudden cold single-roller method;
(3) grind the screening alloy;
(4) in basic solution, after handling, activity obtains the amorphous raney catalyzer.
5, according to the Preparation of catalysts method described in the claim 4, it is characterized in that the Ni in the alloy accounts for 20～60wt%, the add-on of M is 0.1～10wt%, all the other are aluminium.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02150722 CN1421383A (en) | 2002-11-26 | 2002-11-26 | Amorphous skeletal-nickel hydrogenating catalyst for anthraquinone process of preparing hydrogen peroxide and its prepn |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317253C (en) * | 2004-04-29 | 2007-05-23 | 中国石油化工股份有限公司 | Process for hydrogenation of alkyl anthraquinone by using magnetically stabilized bed |
| CN100366527C (en) * | 2004-03-02 | 2008-02-06 | 复旦大学 | High efficient quenching cold nickel catalyst of aqueous hydrogen peroxide solution prepared by 2-ethyl-anthraquinone hydrogenation |
| CN101199934B (en) * | 2006-12-13 | 2010-09-22 | 中国石油化工股份有限公司 | Process for preparing modified amorphous nickel alloy catalyst |
| CN102492865A (en) * | 2011-12-01 | 2012-06-13 | 西北有色金属研究院 | Porous material for purifying high-temperature gas and preparation method thereof |
| CN102658207A (en) * | 2012-04-23 | 2012-09-12 | 陕西开达化工有限责任公司 | High-dispersion palladium catalyst used for anthraquinone hydrogenation and preparation method of same |
| CN103302257A (en) * | 2013-06-07 | 2013-09-18 | 苏州市泰力达科技有限公司 | Preparation method of aniline hydrogenating amorphous nickel-aluminum catalyst |
| CN103495420A (en) * | 2013-09-26 | 2014-01-08 | 昆明理工大学 | Method for preparing ZnO-CuO composite metal oxide powder |
| CN104888783A (en) * | 2014-03-03 | 2015-09-09 | 中国石油化工股份有限公司 | Methanation catalyst, preparation method and application thereof |
| CN106140195A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | The Hydrobon catalyst of caprolactam and the hydrofinishing process of caprolactam |
| CN106140196A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | BYD Hydrogenation for the hydrogenation catalyst of BDO and BYD Hydrogenation for the method for BDO |
| CN107029753A (en) * | 2017-06-06 | 2017-08-11 | 青岛科技大学 | A kind of preparation method of anti-powdering skeletal nickel catalyst |
| CN108264455A (en) * | 2016-12-30 | 2018-07-10 | 中国石油化工股份有限公司 | A kind of method for preparing tetrahydrochysene -2- amyl anthraquinones and a kind of production method of hydrogen peroxide |
-
2002
- 2002-11-26 CN CN 02150722 patent/CN1421383A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366527C (en) * | 2004-03-02 | 2008-02-06 | 复旦大学 | High efficient quenching cold nickel catalyst of aqueous hydrogen peroxide solution prepared by 2-ethyl-anthraquinone hydrogenation |
| CN1317253C (en) * | 2004-04-29 | 2007-05-23 | 中国石油化工股份有限公司 | Process for hydrogenation of alkyl anthraquinone by using magnetically stabilized bed |
| CN101199934B (en) * | 2006-12-13 | 2010-09-22 | 中国石油化工股份有限公司 | Process for preparing modified amorphous nickel alloy catalyst |
| CN102492865A (en) * | 2011-12-01 | 2012-06-13 | 西北有色金属研究院 | Porous material for purifying high-temperature gas and preparation method thereof |
| CN102658207A (en) * | 2012-04-23 | 2012-09-12 | 陕西开达化工有限责任公司 | High-dispersion palladium catalyst used for anthraquinone hydrogenation and preparation method of same |
| CN103302257A (en) * | 2013-06-07 | 2013-09-18 | 苏州市泰力达科技有限公司 | Preparation method of aniline hydrogenating amorphous nickel-aluminum catalyst |
| CN103495420A (en) * | 2013-09-26 | 2014-01-08 | 昆明理工大学 | Method for preparing ZnO-CuO composite metal oxide powder |
| CN103495420B (en) * | 2013-09-26 | 2015-05-20 | 昆明理工大学 | Method for preparing ZnO-CuO composite metal oxide powder |
| CN104888783A (en) * | 2014-03-03 | 2015-09-09 | 中国石油化工股份有限公司 | Methanation catalyst, preparation method and application thereof |
| CN106140195A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | The Hydrobon catalyst of caprolactam and the hydrofinishing process of caprolactam |
| CN106140196A (en) * | 2015-04-22 | 2016-11-23 | 上海迅凯新材料科技有限公司 | BYD Hydrogenation for the hydrogenation catalyst of BDO and BYD Hydrogenation for the method for BDO |
| CN106140196B (en) * | 2015-04-22 | 2019-02-05 | 上海迅凯新材料科技有限公司 | BYD adds the method that hydrogen prepares the hydrogenation catalyst of BDO and BYD adds hydrogen to prepare BDO |
| CN108264455A (en) * | 2016-12-30 | 2018-07-10 | 中国石油化工股份有限公司 | A kind of method for preparing tetrahydrochysene -2- amyl anthraquinones and a kind of production method of hydrogen peroxide |
| CN107029753A (en) * | 2017-06-06 | 2017-08-11 | 青岛科技大学 | A kind of preparation method of anti-powdering skeletal nickel catalyst |
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