CN115999528A - Anthraquinone degradation product regeneration method, regenerated catalyst and preparation thereof - Google Patents

Anthraquinone degradation product regeneration method, regenerated catalyst and preparation thereof Download PDF

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CN115999528A
CN115999528A CN202111232178.5A CN202111232178A CN115999528A CN 115999528 A CN115999528 A CN 115999528A CN 202111232178 A CN202111232178 A CN 202111232178A CN 115999528 A CN115999528 A CN 115999528A
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catalyst
anthraquinone
fluoride
oxide
regenerated catalyst
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张晓昕
王宣
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention discloses an anthraquinone degradation product regenerated catalyst which is characterized by comprising 10-98 wt% of aluminum oxide, 1-80 wt% of magnesium oxide, 1-30 wt% of fluoride and 0-10 wt% of transition metal oxide selected from VIB group and VIIB group on a dry basis and based on the weight of the catalyst. The catalyst can greatly improve the total amount of the effective anthraquinone and effectively improve the recycling rate of the working solution.

Description

Anthraquinone degradation product regeneration method, regenerated catalyst and preparation thereof
Technical Field
The invention relates to an anthraquinone degradation product regeneration, a metal-containing regeneration catalyst and a preparation method of the regeneration catalyst in the technical field of producing hydrogen peroxide by an anthraquinone method.
Background
Hydrogen peroxide (the aqueous solution of which is called hydrogen peroxide) has a molecular formula of H 2 O 2 Is a strong oxidant which can be mixed with water in any ratio and is widely applied to the fields of chemical industry, papermaking, printing and dyeing, environmental protection and the like. In recent years, hydrogen peroxide has been used in large quantities for the production of bulk chemicals such as caprolactam and propylene oxide, and the yield and the dosage thereof have been increasedThe length is very rapid.
Anthraquinone process is currently the main process for the industrial production of hydrogen peroxide. The anthraquinone process of producing hydrogen peroxide is to dissolve the work carrier in organic solvent to form work liquid, and the work liquid is hydrogenated, oxidized and extracted to obtain hydrogen peroxide. The working carrier for producing hydrogen peroxide by the anthraquinone method can be alkylanthraquinone and/or hydrogenated alkylanthraquinone, and the organic solvent is generally a mixed solvent of heavy aromatic hydrocarbon and esters or higher alcohols. In the hydrogenation process, H is used in the presence of a hydrogenation catalyst 2 Hydrogenating the working carrier to generate corresponding alkyl hydro-anthraquinone and/or hydrogenated alkyl hydro-anthraquinone to obtain hydrogenated liquid; in the oxidation process, the hydrogenation solution is contacted with oxygen or air to generate hydrogen peroxide, and simultaneously, the alkyl hydro-anthraquinone and/or the hydrogenated alkyl hydro-anthraquinone are restored into alkyl anthraquinone and/or hydrogenated alkyl anthraquinone; in the extraction process, hydrogen peroxide is extracted from the oxidation liquid by water, and raffinate is recycled to the hydrogenation process after post-treatment.
In the process of producing hydrogen peroxide by the anthraquinone process, some side reactions occur during the hydrogenation and oxidation processes, resulting in degradation of the working carrier, which loses its ability to produce hydrogen peroxide, and the formation of unwanted inert degradants, such as octahydro-anthraquinone, hydroxyanthrone, anthrone, tetrahydroanthraquinone epoxide, etc., with anthrone being the predominant inert degradant. The generation of inert degradation products not only continuously reduces the anthraquinone content in the working solution and reduces the preparation efficiency of hydrogen peroxide, but also causes the change of physical properties of the working solution, such as the reduction of surface tension, the increase of viscosity, the increase of system resistance, the loss of active ingredients and the like, and finally leads to the reduction of hydrogen peroxide yield, the reduction of quality and the increase of production cost, so that the process cannot be normally carried out. Therefore, regeneration of anthraquinone degradation products has been the focus of attention and research. Clay (basic alumina) is widely used in industry to regenerate degradation products. Because the composition of the working solution and the degradation mechanism of the anthraquinone are complex, the generated degradation products are very various, and therefore, it is difficult to search a regenerated catalyst to convert all degradation products into effective anthraquinone. The clay commonly used in industry only can regenerate certain degradation products, the regeneration efficiency is low, and stable production can be kept only by frequently replacing fresh clay, and each time the clay is replaced, the loss of working solution can be caused, and the labor intensity and the production cost are certainly increased. Therefore, it is of great importance to develop a catalyst with high regeneration efficiency.
USP0018013 discloses an H 2 O 2 An industrial catalyst for regenerating anthraquinone degradation products and a preparation method thereof. The method comprises the steps of firstly immersing alumina in a saturated aqueous solution of magnesium salt, precipitating magnesium ions in alumina pores by using an ammonia water solution with pH value of 9-13, and finally roasting at 300-800 ℃ to obtain MgO/Al with concentration of 1-50% 2 O 3 . The method is improved on the basis of the traditional anthraquinone degradation product regenerated catalyst, and has certain application value. However, mgO reacts with water in the anthraquinone working fluid to form hexagonal Mg (OH) in a flake-like morphology 2 The particle size is about 2-3 μm. Therefore, after MgO in alumina pore canal has crystal phase change, the grain size change is obvious, and stress for cracking the alumina pore canal is generated, so that the crushing strength of the catalyst is reduced, the service cycle is shortened, and the production of hydrogen peroxide is seriously influenced.
USP4668499 discloses a process for regenerating aromatic tertiary amines as degradation catalysts in an oxygen atmosphere, which are homogeneous catalysts and can be recycled with the working fluid, mainly for regenerating degradation products resulting from excessive hydrogenation. However, the catalyst has less renewable degradation species, low regeneration efficiency and difficult separation and recovery, and the stability of the aromatic tertiary amine under the harsh conditions of anthraquinone hydrogenation and oxidation is yet to be examined.
CN102728338A provides a solution which can be expressed as MeO/Al 2 O 3 Wherein MeO is any one or more of alkaline earth metal oxides or ZnO. The catalyst has higher regeneration efficiency, but the hydrotalcite precursor is synthesized firstly by a hydrothermal method during preparation, the preparation process is complex, and the preparation cost of the catalyst is higher.
CN106540685A and CN 106629620a provide a method for preparing and regenerating working fluids of alumina-supported anthraquinone degradation products containing at least one metal element ii a and at least one second metal element, which has a better regeneration effect on anthrone degradation products, but has no effect on other degradation products such as hydroxyanthrone and tetrahydroanthraquinone epoxide.
At present, the alumina and the modified alumina have a plurality of defects as anthraquinone degradation product regenerated catalysts: (1) Only partial degradation products can be regenerated, and the degradation products are not completely regenerated; (2) The mechanical strength of the alumina is insufficient, the alumina is easy to pulverize in alkaline working solution, and the burden of alkali separation in the post-treatment process is increased; (3) The system often has the phenomenon of carrying water and alkali during regeneration, and has a certain influence on production. Although it has been proposed to increase the life of regenerated catalysts by adding other solid bases such as Mg and the like, such regenerated catalysts are often prepared with nitrates as precursor salts, and the preparation process is not friendly to the environment, for example, the calcination process generates a large amount of nitrogen oxides to pollute the environment; at the same time, due to Mg (NO 3 ) 2 ·6H 2 O has limited solubility in water, and when preparing high-load solid alkali, the O can be prepared by a high-temperature and repeated impregnation method, so that the manufacturing cost is greatly increased.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide an anthraquinone degradation product regenerated catalyst which is compounded with various alkali strengths and can be used for efficiently regenerating degradation products of different types, and a preparation method and application thereof.
In order to achieve the above object, the first aspect of the present invention provides an anthraquinone degradation product regenerated catalyst characterized in that the catalyst comprises 10 to 98% by weight of alumina, 1 to 80% by weight of magnesia, 1 to 30% by weight of fluoride and 0 to 10% by weight of an oxide of a transition metal M selected from group VIB and VIIB, on a dry basis and based on the weight of the catalyst.
In order to achieve the above object, the second aspect of the present invention also provides a method for preparing a regenerated catalyst of an anthraquinone degradation product, characterized in that the method comprises the steps of:
(1) Dissolving soluble aluminum salt, soluble magnesium salt and optionally soluble compound of transition metal M selected from VIB group and/or VIIB group in deionized water to prepare mixed salt solution;
(2) Adding an alkaline solution into the mixed salt solution to form a precipitate, filtering after the precipitate is completed, washing with water until the pH value is 11-12, and drying to obtain powder;
(3) And (3) fully mixing the powder obtained in the step (2), fluoride and a binder, and forming.
In order to achieve the above object, the third aspect of the present invention further provides a method for regenerating a circulating working fluid in the production of hydrogen peroxide by the anthraquinone process, comprising contacting the circulating working fluid with the above-described anthraquinone degradation product regeneration catalyst provided by the present invention or the anthraquinone degradation product regeneration catalyst obtained by the production method of the present invention to convert anthrone-type, hydroxyanthrone, tetrahydroanthraquinone epoxide and tetrahydro-2-alkylanthraquinone compounds in the circulating working fluid into anthraquinone-type compounds.
The catalyst for regenerating anthraquinone degradation products provided by the invention remarkably improves the capability of converting anthrone, hydroxy anthrone, tetrahydroanthraquinone epoxide and tetrahydro-2-alkyl anthraquinone compounds in circulating working solution into effective anthraquinone compounds, greatly improves the total amount of effective anthraquinone, and effectively improves the recycling rate of the working solution.
Drawings
FIG. 1 is a TPD-CO of regenerated catalyst-1 prepared in example 1 2 A spectrogram.
FIG. 2 is a TPD-CO of clay used in comparative test example 2 2 A spectrogram.
Detailed Description
An anthraquinone degradation product regenerated catalyst, characterized in that the catalyst comprises 10-98 wt.% of alumina, 1-80 wt.% of magnesia, 1-30 wt.% of fluoride and 0-10 wt.% of an oxide of a transition metal M selected from group VIB and VIIB, based on the weight of the catalyst and on a dry basis.
Preferably, the catalyst comprises 30-92 wt.% alumina, 2-10 wt.% fluoride, 5-67 wt.% magnesia and 0.2-8 wt.% oxide of a transition metal M selected from groups VIB, VIIB. More preferably, the catalyst comprises 48-72 wt.% alumina, 4-8 wt.% fluoride, 10-40 wt.% magnesia and 1-6 wt.% oxide of a transition metal M selected from groups VIB, VIIB.
Wherein the fluoride is preferably calcium fluoride, magnesium fluoride or aluminum fluoride. The oxide of the transition metal M of the VIB group is preferably molybdenum oxide or chromium oxide, and the oxide of the transition metal M of the VIIB group is preferably manganese oxide.
The regenerated catalyst is characterized in that the TPD-CO of the catalyst 2 The spectrum has three main peaks representing the weakly basic sites at about 100 ℃, the strongly basic sites at 306 ℃ and the strongly basic sites at 660 ℃ of the oxide, respectively.
The regenerated catalyst can be formed into a spherical catalyst with the particle size of 0.5-5.0 mm and has the strength of 120-190N/particle, preferably 135-170N/particle.
The invention also provides a preparation method of the anthraquinone degradation product regenerated catalyst, which is characterized by comprising the following steps:
(1) Dissolving soluble aluminum salt, soluble magnesium salt and optionally soluble compound of transition metal M selected from VIB group and/or VIIB group in deionized water to prepare mixed salt solution;
(2) Adding an alkaline solution into the mixed salt solution to form a precipitate, filtering after the precipitate is completed, washing with water until the pH value is 11-12, and drying to obtain powder;
(3) And (3) fully mixing the powder obtained in the step (2), fluoride and a binder, and forming.
In the preparation method, the step (1) further comprises the process of ultrasonic oscillation for 1-12h at 30-90 ℃ after the precipitation is complete.
In the preparation method, the fluoride is CaF 2 、MgF 2 And AlF 3 One or more of the following. The alkaline solution is selected from NaOH, KOH, na 2 CO 3 、NaHCO 3 Or a mixture of one or more of ammonia. The group VIB and/or group VIIB transition metal M is at least one selected from tungsten, molybdenum, chromium and manganese. The said processThe soluble compound of the transition metal M in the VIB group and the VIIB group is one or more of sodium tungstate, ammonium tungstate, sodium molybdate, ammonium molybdate, chromium nitrate and manganese nitrate.
The binder binds the aluminum-containing carrier, mgO and oxide powder particles of transition metal M together to improve the strength and the service life of the composite catalyst. If the amount of the binder is insufficient, molding is difficult, and even if molding is performed with difficulty, the binder breaks when leaving the molding machine. When the binder amount is too large, the spherical product becomes soft and tacky. In the present invention, the binder may be at least one selected from the group consisting of an aluminum sol, a silica sol, and water glass, and preferably the binder is an aluminum sol. If silica sol is used as the binder, the silica sol may be acidic silica sol or alkaline silica sol, and may be obtained commercially or prepared according to any one of the prior art. Other inorganic oxide precursors known to those skilled in the art to have binding properties may also be added during the preparation of the composite catalyst.
Preferably, the shaping is a shaping process to obtain a spherical catalyst with a particle size of 0.5-5.0 mm. The optional forming process is to turn into a small ball catalyst in a ball rolling machine, screen out small balls with the diameter of 0.5-5.0 mm in the obtained small ball catalyst, dry and bake the small ball catalyst to obtain the small ball catalyst. The pellet catalyst may be used in a fixed bed reactor or a moving bed reactor. .
In the method provided by the invention, the catalyst precursor after the ball forming may be dried and calcined to improve the strength of the catalyst, and the drying and calcining are well known to those skilled in the art, and for example, the drying conditions may include: the temperature is 80-200 ℃ and the time is 1-10h, and the roasting conditions can include: the temperature is 200-900 ℃ and the time is 0.5-10h.
The invention further provides the anthraquinone degradation product regenerated catalyst obtained by the preparation method.
The invention further provides a regeneration method of circulating working solution in the production of hydrogen peroxide by an anthraquinone method, which comprises the step of contacting the circulating working solution with the anthraquinone degradation product regeneration catalyst provided by the invention and the anthraquinone degradation product regeneration catalyst obtained by the preparation method provided by the invention, so that anthrone type, hydroxy anthrone, tetrahydroanthraquinone epoxide and tetrahydro-2-alkylanthraquinone compounds in the circulating working solution are converted into anthraquinone type compounds.
The regeneration method of the circulating working fluid is characterized in that the circulating working fluid is in contact with a regenerated catalyst, the condition is that the temperature is 20-120 ℃, the pressure is 0-1.5MPa, the pressure is gauge pressure, and the regeneration method is preferred, wherein the temperature is 30-90 ℃, and the pressure is 0-1MPa. The preferred regeneration process is carried out in a fixed bed or moving bed reactor with a circulating working fluid weight hourly space velocity of 1 to 100 hours -1
The present invention is further illustrated by the following detailed description, it being understood that the detailed description described herein is merely illustrative and explanatory of the invention, and is not restrictive of the invention.
In the following examples and comparative examples, the composition of the working fluid and the regenerated working fluid was analyzed by liquid chromatography, which was performed on an Agilent 1260LC type liquid chromatograph equipped with a C18 reverse phase chromatographic column.
The composition of the catalyst was determined by X-ray fluorescence spectroscopy in the following examples and comparative examples.
TPD-CO of catalyst and clay in examples and comparative examples 2 Characterization was performed using an Autochem 2950 chemisorber manufactured by Micromeritic. The testing process comprises the following steps: weighing about 0.1g of sample into a U-shaped sample tube, and loading into a heating furnace; introducing helium gas, heating to 350 ℃, and purging lh at a constant temperature; then cooling the sample to 50 ℃, introducing carbon dioxide after the baseline is stable, and purging lh to the baseline by helium after adsorption saturation; and finally, raising the temperature to 800 ℃ at a heating rate of 15 ℃/min to perform temperature programming desorption.
The catalyst strength in the examples was measured using a DL3 intelligent particle strength tester manufactured by the large Lian Peng hui technology development limited company. The measuring method comprises the following steps: the crushing force values of 150 spherical particles were randomly measured and averaged to give a unit of N.
In the following examples, all reagents used were commercially available ones unless otherwise specified.
In the following examples and comparative examples, the pressures are gauge pressures unless otherwise specified.
Examples 1-7 illustrate regenerated catalysts of the present invention and methods of making the same.
Example 1
(1) 128gMg (NO) 3 ) 2 ·6H 2 O and 375gAl (NO) 3 ) 3 ·9H 2 O is dissolved in 700mL deionized water to prepare magnesium-aluminum mol ratio of 1:2, the mixed salt solution of magnesium nitrate and aluminum nitrate is placed in a constant-temperature water bath at 40 ℃;
(2) Dropwise adding a 20% NaOH solution into the mixed salt solution, regulating the pH value of the mixed solution to be maintained at 11-13, and continuing ultrasonic oscillation for 2 hours under the ultrasonic condition of 60 ℃ after the precipitation is completed; filtering, washing with hot water to pH 7, and drying at 110deg.C for 12 hr; placing the dried powder into a muffle furnace for roasting for 4 hours at 500-800 ℃;
(3) Mixing the mixed powder obtained in the step (2) with 5g CaF 2 30g of aluminum sol (Hunan manufactured by the company Limited, containing 21.5% by weight of Al) 2 O 3 ) Fully and uniformly mixing, rotating into a small ball catalyst in a BY-800 type water chestnut type ball rolling machine (Tiantai pharmaceutical machinery factory in Taizhou, city), screening out small balls with the diameter of 0.5-5.0 mm in the obtained small ball catalyst, drying at 120 ℃ for 4 hours, finally placing a sample in a muffle furnace, programming to be heated to 550 ℃, and roasting at constant temperature for 4 hours to obtain the spherical catalyst-1. The catalyst strength was measured to be 140N/pellet by an intensity measuring instrument.
Catalyst-1 had a composition of 69.7 wt% Al 2 O 3 6.1% by weight of calcium fluoride and 24.2% by weight of MgO.
FIG. 1 is a TPD-CO of catalyst-1 2 A spectrogram. As can be seen from the figure, TPD-CO of catalyst-1 2 The spectrum exhibits three main peaks, a weakly basic (100 ℃) position, a moderately strongly basic (306 ℃) position and a strongly basic (660 ℃) position of the oxide, respectively. While clay has only one moderately strong alkaline site (286 ℃).
Example 2
(1) 128gMg (NO) 3 ) 2 ·6H 2 O、375gAl(NO 3 ) 3 ·9H 2 O and 10g of 50% manganese nitrate aqueous solution were dissolved in 700mL of deionized water to prepare a magnesium aluminum molar ratio of 1:2, the mixed salt solution of magnesium nitrate and aluminum nitrate is placed in a constant-temperature water bath at 40 ℃;
(2) Dropwise adding a 20% NaOH solution into the mixed salt solution, regulating the pH value of the mixed solution to be maintained at 11-13, and continuing ultrasonic oscillation for 2 hours under the ultrasonic condition of 60 ℃ after the precipitation is completed; filtering, washing with hot water to pH 7, and drying at 110deg.C for 12 hr; placing the dried powder into a muffle furnace for roasting for 4 hours at 500-800 ℃;
(3) Mixing the mixed powder obtained in the step (2) with 5g CaF 2 30g of aluminum sol (Hunan manufactured by the company Limited, containing 21.5% by weight of Al) 2 O 3 ) Fully and uniformly mixing, rotating into a small ball catalyst in a BY-800 type water chestnut type ball rolling machine (Tiantai pharmaceutical machinery factory in Taizhou, city), screening out small balls with the diameter of 0.5-5.0 mm in the obtained small ball catalyst, drying at 120 ℃ for 4 hours, finally placing a sample in a muffle furnace, programming to be heated to 550 ℃, and roasting at constant temperature for 4 hours to obtain the spherical catalyst-2. The catalyst strength was measured to be 146N/pellet by an intensity measuring instrument.
Catalyst-2 had a composition of 65.8 wt% Al 2 O 3 5.7 wt% calcium fluoride, 5.6 wt% MnO 2 And 22.9 weight percent MgO.
TPD-CO of catalyst-2 2 The spectrogram has the features of fig. 1.
Example 3
(1) 128gMg (NO) 3 ) 2 ·6H 2 O、375gAl(NO 3 ) 3 ·9H 2 O and 10g of chromium nitrate were dissolved in 700mL of deionized water to prepare a molar ratio of magnesium to aluminum of 1:2, the mixed salt solution of magnesium nitrate and aluminum nitrate is placed in a constant-temperature water bath at 40 ℃;
(2) Dropwise adding a 20% NaOH solution into the mixed salt solution, regulating the pH value of the mixed solution to be maintained at 11-13, and continuing ultrasonic oscillation for 2 hours under the ultrasonic condition of 60 ℃ after the precipitation is completed; filtering, washing with hot water to pH 7, and drying at 110deg.C for 12 hr; placing the dried powder into a muffle furnace for roasting for 4 hours at 500-800 ℃;
(3) Mixing the components obtained in step (2)Mixing the powder with 5g CaF 2 30g of aluminum sol (Hunan manufactured by the company Limited, containing 21.5% by weight of Al) 2 O 3 ) Fully and uniformly mixing, rotating into a small ball catalyst in a BY-800 type water chestnut type ball rolling machine (Tiantai pharmaceutical machinery factory in Taizhou, city), screening out small balls with the diameter of 0.5-5.0 mm in the obtained small ball catalyst, drying at 120 ℃ for 4 hours, finally placing a sample in a muffle furnace, programming to be heated to 550 ℃, and roasting at constant temperature for 4 hours to obtain the spherical catalyst-3. The catalyst strength was measured to be 160N/pellet by an intensity measuring instrument.
Catalyst-3 had a composition of 68.1 wt% Al 2 O 3 5.9 wt% calcium fluoride, 2.3 wt% Cr 2 O 3 And 23.7 weight percent MgO.
TPD-CO of catalyst-3 2 The spectrogram has the features of fig. 1.
Example 4
(1) 128gMg (NO) 3 ) 2 ·6H 2 O and 187.5gAl (NO) 3 ) 3 ·9H 2 O is dissolved in 600mL deionized water to prepare magnesium-aluminum mol ratio of 1:1 and placing the mixed salt solution of magnesium nitrate and aluminum nitrate in a constant-temperature water bath at 40 ℃;
(2) Dropwise adding a 20% NaOH solution into the mixed salt solution, regulating the pH value of the mixed solution to be maintained at 11-13, and continuing ultrasonic oscillation for 2 hours under the ultrasonic condition of 60 ℃ after the precipitation is completed; filtering, washing with hot water to pH 7, and drying at 110deg.C for 12 hr; placing the dried powder into a muffle furnace for roasting for 4 hours at 500-800 ℃;
(3) Mixing the mixed powder obtained in the step (2) with 5g CaF 2 30g of aluminum sol (Hunan manufactured by the company Limited, containing 21.5% by weight of Al) 2 O 3 ) Fully and uniformly mixing, rotating into a small ball catalyst in a BY-800 type water chestnut type ball rolling machine (Tiantai pharmaceutical machinery factory in Taizhou, city), screening out small balls with the diameter of 0.5-5.0 mm in the obtained small ball catalyst, drying at 120 ℃ for 4 hours, finally placing a sample in a muffle furnace, programming to be heated to 550 ℃, and roasting at constant temperature for 4 hours to obtain the spherical catalyst-4. The catalyst strength was measured to be 170N/pellet using an intensity measuring instrument.
Catalyst-4 had a composition of 56.1 wt%Al 2 O 3 8.8% by weight of calcium fluoride and 35.1% by weight of MgO.
TPD-CO of catalyst-4 2 The spectrogram has the features of fig. 1.
Example 5
(1) 128gMg (NO) 3 ) 2 ·6H 2 O and 375gAl (NO) 3 ) 3 ·9H 2 O is dissolved in 700mL deionized water to prepare magnesium-aluminum mol ratio of 1:2, the mixed salt solution of magnesium nitrate and aluminum nitrate is placed in a constant-temperature water bath at 40 ℃;
(2) Dropwise adding a 20% NaOH solution into the mixed salt solution, regulating the pH value of the mixed solution to be maintained at 11-13, and continuing ultrasonic oscillation for 2 hours under the ultrasonic condition of 60 ℃ after the precipitation is completed; filtering, washing with hot water to pH 7, and drying at 110deg.C for 12 hr; placing the dried powder into a muffle furnace for roasting for 4 hours at 500-800 ℃;
(3) Mixing the mixed powder obtained in the step (2) with 5g of MgF 2 30g of aluminum sol (Hunan manufactured by the company Limited, containing 21.5% by weight of Al) 2 O 3 ) Fully and uniformly mixing, rotating into a small ball catalyst in a BY-800 type water chestnut type ball rolling machine (Tiantai pharmaceutical machinery factory in Taizhou, city), screening out small balls with the diameter of 0.5-5.0 mm in the obtained small ball catalyst, drying at 120 ℃ for 4 hours, finally placing a sample in a muffle furnace, programming to be heated to 550 ℃, and roasting at constant temperature for 4 hours to obtain the spherical catalyst-5. The catalyst strength was determined to be 162N/pellet using an intensity meter.
Catalyst-5 composition 69.7 wt% Al 2 O 3 6.1% by weight of magnesium fluoride and 24.2% by weight of MgO.
TPD-CO of catalyst-5 2 The spectrogram has the features of fig. 1.
Example 6
(1) 128gMg (NO) 3 ) 2 ·6H 2 O、375gAl(NO 3 ) 3 ·9H 2 The molar ratio of magnesium to aluminum was 1 by dissolving O and 5g ammonium molybdate in 700mL deionized water: 2, the mixed salt solution of magnesium nitrate and aluminum nitrate is placed in a constant-temperature water bath at 40 ℃;
(2) Dropwise adding a 20% NaOH solution into the mixed salt solution, regulating the pH value of the mixed solution to be maintained at 11-13, and continuing ultrasonic oscillation for 2 hours under the ultrasonic condition of 60 ℃ after the precipitation is completed; filtering, washing with hot water to pH 7, and drying at 110deg.C for 12 hr; placing the dried powder into a muffle furnace for roasting for 4 hours at 500-800 ℃;
(3) Mixing the mixed powder obtained in the step (2) with 5g CaF 2 30g of aluminum sol (Hunan manufactured by the company Limited, containing 21.5% by weight of Al) 2 O 3 ) Fully and uniformly mixing, rotating into a small ball catalyst in a BY-800 type water chestnut type ball rolling machine (Tiantai pharmaceutical machinery factory in Taizhou, city), screening out small balls with the diameter of 0.5-5.0 mm in the obtained small ball catalyst, drying at 120 ℃ for 4 hours, finally placing a sample in a muffle furnace, programming to be heated to 550 ℃, and roasting at constant temperature for 4 hours to obtain the spherical catalyst-6. The catalyst strength was measured to be 146N/pellet by an intensity measuring instrument.
Catalyst-6 composition 66.4 wt% Al 2 O 3 5.8 wt% calcium fluoride, 4.7 wt% MoO 3 And 23.1 weight percent MgO.
TPD-CO of catalyst-6 2 The spectrogram has the features of fig. 1.
Example 7
(1) 128gMg (NO) 3 ) 2 ·6H 2 O and 375gAl (NO) 3 ) 3 ·9H 2 O is dissolved in 700mL deionized water to prepare magnesium-aluminum mol ratio of 1:2, the mixed salt solution of magnesium nitrate and aluminum nitrate is placed in a constant-temperature water bath at 40 ℃;
(2) Dropwise adding a 20% NaOH solution into the mixed salt solution, regulating the pH value of the mixed solution to be maintained at 11-13, and continuing ultrasonic oscillation for 2 hours under the ultrasonic condition of 60 ℃ after the precipitation is completed; filtering, washing with hot water to pH 7, and drying at 110deg.C for 12 hr; placing the dried powder into a muffle furnace for roasting for 4 hours at 500-800 ℃;
(3) Mixing the mixed powder obtained in the step (2) with 5g of AlF 3 30g of aluminum sol (Hunan manufactured by the company Limited, containing 21.5% by weight of Al) 2 O 3 ) Fully and uniformly mixing, turning into small ball catalyst in BY-800 type water chestnut type ball rolling machine (Tiantai pharmaceutical machinery factory in Taizhou, city), and making small ball catalyst with diameter of 0.5-5.0 mmThe balls are screened out, dried for 4 hours at 120 ℃, finally the sample is placed in a muffle furnace, the temperature is programmed to 550 ℃, and the ball-shaped catalyst-7 is obtained after constant temperature roasting for 4 hours. The catalyst strength was measured by an intensity measuring instrument to be 138N/particle.
Catalyst-7 had a composition of 69.7 wt% Al 2 O 3 6.1% by weight of aluminum fluoride and 24.2% by weight of MgO.
TPD-CO of catalyst-7 2 The spectrogram has the features of fig. 1.
The following test examples 1-7 and comparative test examples 1-2 illustrate the anthraquinone degradation product regeneration method.
Test examples 1 to 7
Test examples 1 to 7 illustrate the effect of carrying out the reaction of the anthraquinone degradation product regeneration method in a fixed bed reactor using the catalysts prepared in examples 1 to 7.
A mixed solution of heavy aromatic hydrocarbon containing amyl anthraquinone and diisobutyl methyl alcohol (DIBC) is adopted as a working solution, wherein the working solution comprises 170.0g/L of amyl anthraquinone, 37.4g/L of tetrahydroamyl anthraquinone, 4.5g/L of tetrahydroanthraquinone epoxide, 5.2g/L of hydroxyanthrone and 3.2g/L of anthrone. 20g of catalyst is weighed and filled into a stainless steel fixed bed with the inner diameter of 10mm, working solution is lifted by a metering pump and flows through the catalyst bed from the bottom of the reactor after being metered, and the space velocity is 1.8h -1 The reaction temperature is 60 ℃, and sampling analysis is carried out after the reaction is carried out for 6 hours. The quantitative analysis was performed by detecting each component in the absorption liquid by HPLC, and the results are shown in Table 1.
Comparative test example 1
The evaluation conditions were the same as in test example 1 without using a catalyst.
Comparative test example 2
The evaluation conditions were the same as those of test example 1 using clay as a catalyst. FIG. 2 is a TPD-CO of clay used in comparative test 2 2 A spectrogram.
TABLE 1
Figure BDA0003316425450000121
As can be seen from the effect of the catalysts prepared in examples 1 to 7 of Table 1 on the reaction of the regeneration method of anthraquinone degradation products, the catalyst of the present invention can almost completely convert degradation products of anthrone compounds, has good conversion performance for epoxide type degradation products, and can simultaneously convert more tetrahydroanthraquinone into corresponding alkylanthraquinone due to the composite alkaline material (weak, medium strong alkali, strong alkaline site) and high crushing strength. Therefore, the regeneration method of the anthraquinone degradation product can greatly improve the total amount of the effective anthraquinone and effectively improve the recycling rate of the working solution.

Claims (21)

1. An anthraquinone degradation product regenerated catalyst, characterized in that the catalyst comprises 10-98 wt.% of alumina, 1-80 wt.% of magnesia, 1-30 wt.% of fluoride and 0-10 wt.% of an oxide of a transition metal M selected from group VIB and VIIB, based on the weight of the catalyst and on a dry basis.
2. The regenerated catalyst according to claim 1 wherein the catalyst comprises 30-92 wt.% alumina, 2-10 wt.% fluoride, 5-67 wt.% magnesia and 0.2-8 wt.% oxide of a transition metal M selected from group VIB, VIIB.
3. The regenerated catalyst according to claim 2 wherein the catalyst comprises 48-72 wt.% alumina, 4-8 wt.% fluoride, 10-40 wt.% magnesia and 1-6 wt.% oxide of a transition metal M selected from group VIB, VIIB.
4. A regenerated catalyst according to any one of claims 1 to 3 wherein the fluoride is one or more of calcium fluoride, magnesium fluoride and aluminium fluoride.
5. A regenerated catalyst according to any one of claims 1 to 3 wherein the oxide of transition metal M of group VIB is molybdenum oxide or chromium oxide and the oxide of transition metal M of group VIIB is manganese oxide.
6. According to claim 1Is characterized in that the TPD-CO of the catalyst 2 The spectrum has three main peaks representing weak alkaline sites at about 100 ℃, medium alkaline sites at 306 ℃ and strong alkaline sites at 660 ℃ of the oxide, respectively.
7. The regenerated catalyst according to claim 1, characterized in that the catalyst is a spherical catalyst having a particle size of 0.5 to 5.0 mm.
8. The regenerated catalyst according to claim 7 wherein the catalyst has a strength of 120N/pellet to 190N/pellet.
9. The regenerated catalyst according to claim 8 wherein the catalyst has a strength of 135N/pellet to 170N/pellet.
10. A preparation method of an anthraquinone degradation product regenerated catalyst is characterized by comprising the following steps:
(1) Dissolving soluble aluminum salt, soluble magnesium salt and optionally soluble compound of transition metal M selected from VIB group and/or VIIB group in deionized water to prepare mixed salt solution;
(2) Adding an alkaline solution into the mixed salt solution to form a precipitate, filtering after the precipitate is completed, washing with water until the pH value is 11-12, and drying to obtain powder;
(3) And (3) fully mixing the powder obtained in the step (2), fluoride and a binder, and forming.
11. The preparation method of claim 10, wherein the step (1) further comprises a process of ultrasonic vibration at 30-90 ℃ for 1-12 hours after the precipitation is completed.
12. The process according to claim 10, wherein the fluoride compound in the step (3) is CaF 2 、MgF 2 And AlF 3 One or more of the following.
13. The process according to claim 10, wherein the alkaline solution in step (2) is selected from NaOH, KOH, na 2 CO 3 、NaHCO 3 Or a mixture of one or more of ammonia.
14. The preparation method according to claim 10, wherein the transition metal M is at least one selected from tungsten, molybdenum, chromium and manganese.
15. The preparation method of claim 10, wherein the soluble compound of the transition metal M is one or more of sodium tungstate, ammonium tungstate, sodium molybdate, ammonium molybdate, chromium nitrate and manganese nitrate.
16. The method of claim 10, wherein the binder is an aluminum sol.
17. The method of claim 10, further comprising drying and firing steps after the shaping, the drying comprising: the temperature is 80-200 ℃ and the time is 1-10h, and the roasting comprises the following steps: the temperature is 200-900 ℃ and the time is 0.5-10h.
18. An anthraquinone degradation product regenerated catalyst obtained by the preparation method according to any one of claims 10 to 17.
19. A method for regenerating a circulating working fluid in the production of hydrogen peroxide by the anthraquinone process, which comprises contacting the circulating working fluid with the catalyst for regenerating an anthraquinone degradation product according to any one of claims 1 to 9 and 18 to convert anthrone-type, hydroxyanthrone-type, tetrahydroanthraquinone epoxide-type and tetrahydro-2-alkylanthraquinone-type compounds in the circulating working fluid into anthraquinone-type compounds.
20. The regeneration process of claim 19, wherein the contacting is at a temperature of 20-120 ℃ and a pressure of 0-1.5MPa, the pressure being gauge pressure.
21. The regeneration process according to claim 20, wherein the temperature is 30-90 ℃ and the pressure is 0-1MPa.
CN202111232178.5A 2021-10-22 2021-10-22 Anthraquinone degradation product regeneration method, regenerated catalyst and preparation thereof Pending CN115999528A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020147364A1 (en) * 2001-02-15 2002-10-10 Syvret Robert George Active fluoride catalysts for fluorination reactions
CN1762578A (en) * 2005-09-28 2006-04-26 茂名学院 Supported solid alkali catalyst for synthesis of propylene glycol
CN1962824A (en) * 2006-12-01 2007-05-16 湘潭大学 Process for preparing supported solid catalyst for use in production of bio-diesel oil
CN102133544A (en) * 2010-01-25 2011-07-27 中国石油化工股份有限公司 Alkaline-earth metal fluoride modified alumina supporter, preparation method thereof, and silver catalyst made from alumina supporter and application of silver catalyst in ethylene epoxide (EO) production
CN111097533A (en) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 Solid base catalyst and preparation method and application thereof
CN113441133A (en) * 2020-03-27 2021-09-28 中国石油化工股份有限公司 Catalyst for regenerating anthraquinone degradation product and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020147364A1 (en) * 2001-02-15 2002-10-10 Syvret Robert George Active fluoride catalysts for fluorination reactions
CN1762578A (en) * 2005-09-28 2006-04-26 茂名学院 Supported solid alkali catalyst for synthesis of propylene glycol
CN1962824A (en) * 2006-12-01 2007-05-16 湘潭大学 Process for preparing supported solid catalyst for use in production of bio-diesel oil
CN102133544A (en) * 2010-01-25 2011-07-27 中国石油化工股份有限公司 Alkaline-earth metal fluoride modified alumina supporter, preparation method thereof, and silver catalyst made from alumina supporter and application of silver catalyst in ethylene epoxide (EO) production
CN111097533A (en) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 Solid base catalyst and preparation method and application thereof
CN113441133A (en) * 2020-03-27 2021-09-28 中国石油化工股份有限公司 Catalyst for regenerating anthraquinone degradation product and preparation method thereof

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