CN111389467B - Limestone-gypsum wet desulphurization catalyst - Google Patents

Limestone-gypsum wet desulphurization catalyst Download PDF

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CN111389467B
CN111389467B CN202010197673.6A CN202010197673A CN111389467B CN 111389467 B CN111389467 B CN 111389467B CN 202010197673 A CN202010197673 A CN 202010197673A CN 111389467 B CN111389467 B CN 111389467B
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ceo
limestone
organic alkali
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CN111389467A (en
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齐雷
颜世达
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Hebei Zhonglei New Energy Technology Co ltd
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/508—Sulfur oxides by treating the gases with solids
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/31—Aluminium

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Abstract

The invention relates to the technical field of catalysts, in particular to a limestone-gypsum wet desulphurization catalyst, which comprises a carrier and an active component loaded on the carrier, wherein the carrier comprises CeO treated by an organic alkali solution2‑Al2O3Carrier and CeO2Accounting for 0.2-2.0% of the weight of the carrier; the active component comprises tetra-amino aluminum phthalocyanine, and the active component accounts for 4.6-6.6% of the catalyst by weight percent; and the catalyst is lanthanum modified. The catalyst has uniform particle size and higher specific surface area, can obviously improve the desulfurization efficiency of limestone-gypsum wet desulfurization after introducing La rare element, has denitration capability, is harmless to equipment after long-term use, has no negative effect on a desulfurization system, improves the dehydration rate of gypsum, shortens the dehydration time, and can also improve the quality of gypsum.

Description

Limestone-gypsum wet desulphurization catalyst
Technical Field
The invention relates to the technical field of catalysts, in particular to a limestone-gypsum wet desulphurization catalyst.
Background
The limestone-gypsum wet coal-fired boiler Flue Gas Desulfurization (FGD) process is a preferred desulfurization process of the coal-fired power plant in China due to large flue gas treatment capacity in unit time, no secondary pollution, mature process, rich desulfurizer source and lower price, and more than 90 percent of desulfurization systems of the coal-fired power plant in China adopt the limestone-gypsum wet coal-fired boiler Flue Gas Desulfurization (FGD) process. In recent years, with the increasing national requirements for atmospheric emission of coal-fired, thermal and electric enterprises, the desulfurization efficiency and SO of the coal-fired, thermal and electric enterprises 2The discharge amount becomes whether the power plant can normally produceImportant assessment indexes are that in order to reach new emission standards, two ways are generally adopted to enable a desulfurization system to meet requirements. One is to expand and modify the existing desulfurization system, and the other is to add other auxiliary materials (such as a synergist, an additive, a catalyst and the like).
The capacity expansion modification of the desulfurization system is generally based on the capacity expansion modification of an absorption tower, and meanwhile, the modification of corresponding public systems such as a limestone preparation and storage system, a gypsum dehydration system and the like is carried out, and the modification is all-round. The modification method is to increase SO by increasing the volume of the absorption tower2The physical contact area with limestone slurry is increased to improve the desulfurization efficiency without increasing the SO on the unit of specific surface area2The modification cost reaches millions or even tens of millions for each percentage improvement of the desulfurization efficiency, and the later increased operation cost is very high, thereby causing great economic burden to the power plant. The other way is to add other auxiliary materials, and the idea of the auxiliary materials in the current market is to basically add CaCO3SO that it can react with more SO 2Reaction, thereby improving the desulfurization efficiency and reducing SO2Is discharged. Based on the idea, other similar products in the market are all strong-acid (the pH value is between 1.0 and 3.0). Such auxiliary materials, which have some effect in case of temporary emergencies, are seriously harmful in long-term use: the efficiency is short, the efficiency is low, and the long-term requirement of a power plant on environmental protection cannot be met; the slurry has certain corrosivity on local equipment of a desulfurization system and also causes the slurry to be poisoned; the aerosol is easy to generate and blocks a demister, a pipeline and a nozzle of a desulfurization system; some products have strong odor, causing personal injury and polluting the air.
The above background disclosure is only for the purpose of assisting understanding of the inventive concept and technical solutions of the present invention, and does not necessarily belong to the prior art of the present patent application, and should not be used for evaluating the novelty and inventive step of the present application in the case that there is no clear evidence that the above content is disclosed at the filing date of the present patent application.
Disclosure of Invention
The invention aims to provide a limestone-gypsum wet desulphurization catalyst which has uniform particle size and higher specific surface area, can obviously improve the desulphurization efficiency of limestone-gypsum wet desulphurization after introducing La rare element, has denitration capability, is harmless to equipment after long-term use, has no negative effect on a desulphurization system, improves the gypsum dehydration rate, shortens the dehydration time and can also improve the gypsum quality.
The technical means of the present invention for achieving the above object includes the following items [1] to [20 ].
[1] A limestone-gypsum wet desulphurization catalyst comprises a carrier and an active component carried on the carrier, wherein,
the carrier comprises CeO treated by organic alkali solution2-Al2O3Carrier, and CeO2Accounting for 0.2-2.0% of the weight of the carrier;
the active component comprises tetraaminoaluminum phthalocyanine (AlClPc (NH)2)4) In addition, the active component accounts for 4.6-6.6% of the tetraamino phthalocyanine aluminum in percentage by weight of the catalyst;
and the catalyst is lanthanum modified.
Supported catalyst (La-AlClPc (NH) according to the invention2)4/CeO2-Al2O3Catalyst) can obviously improve the desulfurization efficiency of limestone-gypsum wet desulfurization, and reduces SO in flue gas by using the supported catalyst of the invention on the premise of no reconstruction and expansion of original facilities, no change of original process and no change of original operation2The resistance of mass transfer from gas phase to liquid phase makes a great deal of CaCO3Is converted into CaO due to CaO and SO2The reaction speed of the catalyst is far higher than that of CaCO3With SO2SO as to react with SO sufficiently in the limited time of the flue gas flowing through the absorption tower2Reaction occurs, thereby improving the desulfurization efficiency; the supported catalyst has moderate acidity and alkalinity, meets the pH value requirement of limestone slurry, has stable properties after being completely dissolved in the slurry, does not produce other substances, and does not produce aerosol " The harmful substances which block pipelines, nozzles and demisters are not used for a long time, the negative effect on a desulfurization system is avoided, the gypsum dehydration rate is improved, the dehydration time is shortened, the action time is long, the using amount is small, the energy consumption is reduced to a certain extent, and the quality of byproduct gypsum is improved.
[2]Item [1]]CeO in the catalyst2-Al2O3The preparation method of the carrier comprises the following steps: uniformly mixing pseudo-boehmite dry powder, sesbania powder and dilute nitric acid solution containing cerium nitrate, extruding the mixture into strips, drying the strips at 80-120 ℃ for 6-10 h, and roasting the strips at 500-600 ℃ for 3-5 h to obtain CeO2-Al2O3And (3) a carrier.
[3] In the method of item [2], the weight ratio of the cerium nitrate to the dilute nitric acid solution, the pseudo-boehmite dry powder and the sesbania powder is 1: 80-120: 60-100: 1-2.
[4] In the method according to item [2] or [3], the mass fraction of the dilute nitric acid solution is 1.5 to 3.0 wt%.
[5]Item [1]]～[4]Organic base solution treated CeO in any one of the catalysts2-Al2O3The carrier comprises the following specific steps: subjecting the prepared CeO2-Al2O3Soaking the carrier in a solution containing organic alkali, then washing the carrier to be neutral, and drying the carrier for 2 to 5 hours at the temperature of 80 to 120 ℃ to obtain CeO treated by the organic alkali solution2-Al2O3And (3) a carrier.
[6] The mass fraction of the organic alkali solution in the catalyst according to any one of items [1] to [5] is 4.5 to 12.0 wt%.
[7] The catalyst according to any one of items [1] to [6], wherein the organic base is at least one selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, glycol amine, methyl ethanolamine and ethylenediamine.
[8] The method for producing tetraaminoaluminum phthalocyanine in the catalyst according to any one of items [1] to [7] comprises the steps of:
1) stirring, sequentially adding 4-nitrophthalic anhydride, aluminum sulfate, (NH)4)6Mo2O7、NH4Adding Cl and urea into a large amount of nitrobenzene, performing reflux reaction for 6-8 h at 185-195 ℃, standing and coolingCooling to room temperature;
2) filtering nitrobenzene in the product obtained in the step 1), drying and grinding a filter cake until the filter cake is at least 200 meshes, refluxing for 4-8 h at 60-70 ℃ through distilled water, trichloromethane and ethanol in sequence, and filtering while the solution is hot;
3) drying and grinding the filter cake obtained in the step 2) until the filter cake is at least 200 meshes, refluxing for 2-3 h at 55-60 ℃ by using a potassium tert-butoxide solution with the weight of 30-100 times of that of the filter cake, standing, cooling to room temperature, filtering, drying the filter cake and grinding until the filter cake is at least 200 meshes;
4) adding the product obtained in the step 3) into DMF (dimethyl formamide), and adding 40-100 wt% of Na into the product under stirring2S, refluxing for 6-8 h at the temperature of 60-65 ℃, standing, cooling to room temperature, filtering, drying and grinding a filter cake until the filter cake is at least 200-mesh sieved, refluxing for at least 4h by deionized water, filtering, washing by the deionized water until a washing liquid is neutral, and drying in vacuum to obtain the filter cake.
The method for preparing the tetraaminophthalocyanine aluminum has simple operation, particularly can obviously avoid product loss by refluxing the product with potassium tert-butoxide solution, has high product yield which can reach more than 50 percent, and determines the tetraaminophthalocyanine aluminum (the molecular formula is C) by a German Elementar elemental analyzer36H36AlClN12The content measurement values of the three elements of carbon, hydrogen and nitrogen in the molecule with the structural formula shown in formula (1) are C-61.56, H-5.35 and N-24.11, and the content measurement values are basically close to the theoretical values of C-61.84, H-5.19 and N-24.04 of the three elements of carbon, hydrogen and nitrogen in the molecule.
Figure 728848DEST_PATH_IMAGE001
(1)
[9]Item [8]]4-nitrophthalic anhydride, aluminum sulfate, (NH) in step 1) of the process for the preparation of tetraaminoaluminum phthalocyanine4)6Mo2O7、NH4The addition amount of Cl and urea is 2.5-5.0: 1.1-1.5: 0.05-0.3: 1.
[10] The method for producing tetraaminophthalocyanine aluminum according to item [8] or [9], wherein the weight ratio of distilled water, chloroform and ethanol to the filtrate dry powder in step 2) is 50 to 100:20 to 100: 1.
[11] The method for producing an aluminum tetraaminophthalocyanine according to any one of items [8] to [10], wherein the concentration of the potassium tert-butoxide solution in step 3) is 0.01 to 0.3mol/L, preferably 0.05 to 0.15 nol/L.
[12] The amount of DMF used in step 4) of the process for producing tetraaminophthalocyanine aluminum according to any one of items [8] to [11] is 50 to 200 times by weight the amount of DMF used in the step 3).
[13] The method for producing tetraaminoaluminum phthalocyanine according to any one of items [8] to [12], wherein the weight ratio of the deionized water to the dry filtrate powder in the step 4) of the refluxing filtrate powder is 50 to 200: 1.
[14]Item [1]]～[13]CeO treated with an organic alkali solution in any one of the catalysts2-Al2O3The method for loading the active component tetra-amino aluminum phthalocyanine on the carrier comprises the following steps:
1) dissolving tetra-amino aluminum phthalocyanine in a large amount of DMF at a frequency of 62-70 KHz and a strength of 0.5-0.8 w/cm2The ultrasonic wave is vibrated and dissolved for at least 1h, so that the mixture is uniformly dissolved;
2) CeO treated with organic alkali solution2-Al2O3Roasting the carrier at the temperature of 240-280 ℃ for at least 3h, cooling to room temperature, putting into the mixed solution in the step 1), performing ultrasonic treatment for at least 45min, and performing magnetic stirring for 24 h;
3) filtering the mixed solution obtained in the step 2), taking the filtrate, sequentially washing the filtrate with DMF (dimethyl formamide) and deionized water to be colorless, then washing the filtrate with methanol and ethanol for at least 4 times, and drying the filtrate in vacuum at the temperature of 102-110 ℃ for at least 24 hours to obtain the CeO loaded with tetraaminophthalocyanine aluminum2-Al2O3Catalyst (AlClPc (NH)2)4/CeO2-Al2O3)。
[15]Item [14 ]]In the method, tetraaminophthalocyanine aluminum and CeO treated by organic alkali solution2-Al2O3The weight part of the carrier is controlled to be 1: 5-6.
[16] The catalyst according to any one of items [1] to [15], wherein the method for modifying the catalyst with lanthanum comprises:
1) Dissolving lanthanum chloride in deionized water, and performing ultrasonic oscillation to obtain a lanthanum chloride solution;
2) the prepared AlClPc (NH)2)4/CeO2-Al2O3Soaking the catalyst in a lanthanum chloride solution, magnetically stirring, heating in an oil bath for reaction for at least 5h, centrifuging, evaporating water, and calcining at 125-160 ℃ for at least 2h under vacuum to obtain La-AlClPc (NH)2)4/CeO2-Al2O3A catalyst. La-AlClPc (NH) prepared by the invention2)4/CeO2-Al2O3The catalyst has a particle size of about 30 μm, a pore diameter of about 3nm, and a specific surface area of not less than 195m2The catalyst has the advantages that the catalyst is prepared by introducing La rare elements, the catalytic effect of the prepared catalyst is greatly improved by modification methods such as ultrasonic solubilization, magnetic stirring, low-temperature calcination under vacuum, sample preparation and particle size limitation in the preparation process, the desulfurization efficiency is remarkably improved, certain denitration capability is realized, the catalyst does not have strong acidity, the catalyst is stable in properties after being dissolved in slurry, other substances are not produced, harmful substances such as aerosol and the like which block pipelines, nozzles and demisters are not generated, the catalyst has no negative effect on a desulfurization system after long-term use, the gypsum dehydration rate is improved, the dehydration time is shortened, the action time is long, the dosage is small, the energy consumption is reduced to a certain extent, and the quality of byproduct gypsum is improved.
[17]Item [16 ] ]In the method for modifying the catalyst by lanthanum, the ultrasonic frequency of the step 1) is 42-65 KHz, and the ultrasonic intensity is 0.46-0.55 w/cm2The ultrasonic oscillation time is not less than 2 h.
[18] The method for modifying a catalyst with lanthanum according to item [16] or [17], wherein the lanthanum chloride solution in the step 1) contains 0.01 to 0.3mol/L of lanthanum, preferably 0.1 to 0.2mol/L of lanthanum, and more preferably 0.15 to 0.2mol/L of lanthanum.
[19] The method for modifying a catalyst with lanthanum according to any one of items [16] to [18], wherein the oil bath temperature in the step 2) is 105 to 110 ℃.
[20] Use of the catalyst according to any one of items [1] to [19] in limestone-gypsum wet desulfurization.
The invention has the beneficial effects that:
1) the supported catalyst La of the present invention-AlClPc(NH2)4/CeO2-Al2O3The particle diameter is about 30 μm, the pore diameter is about 3nm, and the specific surface area is not less than 195m2The La rare element is introduced, and the catalytic effect of the prepared catalyst is greatly improved by modification methods such as ultrasonic solubilization, magnetic stirring, low-temperature calcination in vacuum, sample preparation and particle size limitation in the preparation process, so that the desulfurization efficiency is remarkably improved, and the catalyst has certain denitration capacity;
2) the desulfurization efficiency of limestone-gypsum wet desulfurization can be obviously improved, and the supported catalyst of the invention is used for reducing SO in flue gas on the premise of no reconstruction and expansion of original facilities, no change of original process and no change of original operation 2The resistance of mass transfer from gas phase to liquid phase makes a great deal of CaCO3Is converted into CaO due to CaO and SO2The reaction speed of the catalyst is far higher than that of CaCO3With SO2SO as to react with SO sufficiently in the limited time of the flue gas flowing through the absorption tower2Reaction occurs, thereby improving the desulfurization efficiency;
3) the supported catalyst has moderate acidity and alkalinity, meets the requirement of pH value of limestone slurry, has stable properties after being completely dissolved in the slurry, does not produce other substances, does not generate harmful substances such as aerosol and the like which block pipelines, nozzles and demisters, has no negative effect on a desulfurization system after long-term use, improves the dehydration rate of gypsum, shortens the dehydration time, has long action time and small dosage, reduces energy consumption to a certain extent, and improves the quality of byproduct gypsum.
The invention adopts the technical scheme to provide the model essay, makes up the defects of the prior art, and has reasonable design and convenient operation.
Drawings
In order to make the aforementioned and other objects, features, and advantages of the invention, as well as others which will become apparent, reference is made to the following description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic view of the molecular structure of tetraaminoaluminum phthalocyanine according to the present invention;
FIG. 2 is a schematic view showing a process for preparing tetraaminoaluminum phthalocyanine in example 1 of the present invention;
FIG. 3 is an infrared spectrum of aluminum tetraaminophthalocyanine in example 1 of the present invention;
FIG. 4 is a schematic view showing the continuous desulfurization of the desulfurization catalyst in example 1 of the present invention.
Detailed Description
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The present invention uses the methods and materials described herein; other suitable methods and materials known in the art may be used. The materials, methods, and examples described herein are illustrative only and are not intended to be limiting. All publications, patent applications, patents, provisional applications, database entries, and other references mentioned herein, and the like, are incorporated by reference herein in their entirety. In case of conflict, the present specification, including definitions, will control.
All percentages, parts, ratios, etc., are by weight unless otherwise indicated; "wt%" means weight percent; "mol%" means mole percent.
Herein, the term "made from … …" is equivalent to "comprising". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting essentially of … …" is used to define a composition, method, or apparatus that contains additional materials, steps, features, components, or elements in addition to those literally described, provided that such additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristics of the claimed invention. The term "consisting essentially of … …" is in the intermediate zone between "comprising" and "consisting of … …".
The term "comprising" is intended to include embodiments encompassed by the terms "consisting essentially of … …" and "consisting of … …". Similarly, the term "consisting essentially of … …" is intended to include embodiments encompassed by the term "consisting of … …".
When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when describing a range of "1 to 5," the described range should be understood to include ranges of "1 to 4," "1 to 3," "1 to 2 and 4 to 5," "1 to 3 and 5," and the like. Where a range of numerical values is described herein, unless otherwise stated, the range is intended to include the endpoints of the range, and all integers and fractions within the range.
When the term "about" is used to describe a numerical value or an end point of a range, the disclosure should be understood to include the specific value or end point referred to.
Furthermore, "or" means "or" unless expressly stated to the contrary, rather than "or" exclusively. For example, either of the following conditions applies to condition a "or" B: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), and both a and B are true (or present).
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to mean no limitation on the number of occurrences (i.e., occurrences) of the element or component. Thus, "a" or "an" should be understood to include one or at least one and the singular forms of an element or component also include the plural unless the singular is explicitly stated.
The materials, methods, and examples described herein are illustrative only and not intended to be limiting unless otherwise specified. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.
The present invention is described in detail below.
Example 1: a limestone-gypsum wet desulphurization catalyst:
a limestone-gypsum wet desulphurization catalyst comprises a carrier and an active component carried on the carrier, wherein,
the carrier comprises CeO treated by organic alkali solution2-Al2O3Carrier, and CeO21.5 percent of the weight of the carrier;
the active component comprises tetraaminoaluminum phthalocyanine (AlClPc (NH)2)4) And the active component accounts for 5.0 percent of the weight of the catalyst, and the tetraaminophthalocyanine aluminum accounts for 5.0 percent of the weight of the catalyst;
and the catalyst is lanthanum modified.
The limestone-gypsum wet desulphurization catalyst is prepared by the following steps:
1. preparation of organic alkali solution-treated CeO2-Al2O3Carrier:
1.1, uniformly mixing the pseudo-boehmite dry powder, sesbania powder and dilute nitric acid solution containing cerium nitrate, extruding and forming, drying at 100 ℃ for 8 hours, and roasting at 525 ℃ for 4 hours to obtain CeO2-Al2O3A carrier;
1.2 preparation of CeO2-Al2O3Soaking the carrier in solution containing organic alkali, washing with water to neutrality, and drying at 110 deg.C for 4 hr to obtain CeO treated with organic alkali solution2-Al2O3A carrier;
in addition to this, the present invention is,
in the step 1.1, the weight ratio of the cerium nitrate to the dilute nitric acid solution to the pseudo-boehmite dry powder to the sesbania powder is 1:100:80: 2;
In the step 1.1, the mass fraction of the dilute nitric acid solution is 2.0 wt%;
in the step 1.2, the mass fraction of the organic alkali solution is 5.0 wt%;
the organic base in step 1.2 is diethanolamine.
2. Preparation of tetra-amino aluminum phthalocyanine:
2.1, stirring, sequentially adding 4-nitrophthalic anhydride, aluminum sulfate, (NH)4)6Mo2O7、NH4Adding Cl and urea into a large amount of nitrobenzene, carrying out reflux reaction at 189 ℃ for 6h, standing and cooling to room temperature;
2.2, filtering out nitrobenzene in the product in the step 1), drying and grinding a filter cake until the filter cake is sieved by a 300-mesh sieve, refluxing for 6 hours at 68 ℃ through distilled water, chloroform and ethanol respectively in sequence, and filtering while the solution is hot;
2.3, drying and grinding the filter cake obtained in the step 2) to a 300-mesh sieve, refluxing for 3h at 58 ℃ by using a potassium tert-butoxide solution 60 times the weight of the filter cake, standing, cooling to room temperature, filtering, drying the filter cake, and grinding to a 300-mesh sieve;
2.4 addition of the product of step 3) to DMF and stirring addition of 50% by weight Na2S, refluxing for 6 hours at the temperature of 65 ℃, standing, cooling to room temperature, filtering, drying and grinding a filter cake to a size of 300 meshes, refluxing for 4 hours by using deionized water, filtering, washing by using the deionized water until a washing liquid is neutral, and drying in vacuum to obtain the filter cake;
in addition to this, the present invention is,
in step 2.1, 4-nitrophthalic anhydride, aluminum sulfate, (NH) 4)6Mo2O7、NH4The addition amount of Cl and urea is 5.0:1.5:0.1: 1;
in the step 2.2, the weight ratio of the distilled water, the trichloromethane and the ethanol to the dry powder of the filtrate is 100:40:80: 1;
in the step 2.3, the concentration of the potassium tert-butoxide solution is 0.05 mol/L;
the amount of DMF used in step 2.4 is 60 times the weight of the product of step 2.3;
in the step 2.4, the weight ratio of the deionized water of the backflow filtrate dry powder to the filtrate dry powder is 100: 1;
the scheme for preparing tetra-amino aluminum phthalocyanine is shown in figure 2.
3. Loading:
3.1 dissolving tetra-amino-phthalocyanine aluminium in a large amount of DMF at a frequency of 65KHz and an intensity of 0.6w/cm2The ultrasonic wave is oscillated and dissolved for 2 hours to ensure that the mixture is uniformly dissolved;
CeO 3.2 and 5 times of that of tetraaminoaluminum phthalocyanine treated by organic alkali solution2-Al2O3Roasting the carrier at 265 ℃ for 3h, cooling to room temperature, putting into the mixed solution in the step 1), and performing magnetic stirring for 24h after performing ultrasonic treatment for 60 min;
3.3 filtering the mixed solution obtained in the step 2), taking the filtrate, sequentially washing the filtrate by using DMF (dimethyl formamide) and deionized water to be colorless, then washing the filtrate for 4 times by using methanol and ethanol, and drying the filtrate in vacuum at the temperature of 108 ℃ for 48 hours to obtain the CeO loaded with tetraaminophthalocyanine aluminum2-Al2O3Catalyst (AlClPc (NH)2)4/CeO2-Al2O3)。
4. Lanthanum modification:
4.1, dissolving lanthanum chloride in deionized water, and carrying out ultrasonic oscillation to obtain a lanthanum chloride solution;
4.2 preparing AlClPc (NH)2)4/CeO2-Al2O3Soaking the catalyst in lanthanum chloride solution, magnetically stirring, heating in oil bath for 5 hr, centrifuging, evaporating water, and vacuum calcining at 150 deg.C for 5 hr to obtain La-AlClPc (NH)2)4/CeO2-Al2O3A catalyst;
in addition to this, the present invention is,
the ultrasonic frequency of the step 4.1 is 45KHz, and the ultrasonic intensity is 0.5w/cm2Ultrasonic oscillation is carried out for 3 hours;
the lanthanum content in the lanthanum chloride solution in the step 4.1 is 0.2 mol/L;
the oil bath temperature for step 4.2 was 108 ℃.
Experimental example 1: structural analysis of tetraaminophthalocyanine aluminum:
the infrared spectrum of tetraaminoaluminum phthalocyanine is shown in figure 3, 3446cm-1The absorption peak is induced by O-H stretching vibration due to phthalocyanine molecule absorbing water molecule, 2912cm-1The absorption peak is due to the elongation of the amino groupCaused by contraction vibration, at 740cm-1、1639cm-1And 1468cm-1The absorption peaks occur due to the absorption of vibrations of the two aromatic rings in the phthalocyanine ring.
Example 2: another limestone-gypsum wet desulfurization catalyst:
this example provides another limestone-gypsum wet desulfurization catalyst, the formulation and preparation method of which are substantially similar to those of example 1, and the difference between this example and example 1 is that the CeO2-Al2O3The carrier is not treated with an organic base solution.
Example 3: another limestone-gypsum wet desulfurization catalyst:
this example provides another limestone-gypsum wet desulphurization catalyst, the formulation and preparation method of which are substantially similar to those of example 1, and the difference between this example and example 1 is that the CeO2-Al2O3CeO in the carrier2Accounting for 0.1 percent of the weight of the carrier.
Example 4: another limestone-gypsum wet desulfurization catalyst:
this example provides another limestone-gypsum wet desulfurization catalyst, the formulation and preparation method of which are substantially similar to those of example 1, and the difference between this example and example 1 is that γ -Al is used2O3Carrier instead of CeO2-Al2O3The gamma-Al2O3The carrier particle diameter is 34 μm, the pore diameter is 3.92nm, and the specific surface area is 232m2(ii)/g, available from Tianjin Yueli chemical Co., Ltd.
Example 5: another limestone-gypsum wet desulfurization catalyst:
this example provides another limestone-gypsum wet desulfurization catalyst, the formulation and preparation method of which are substantially similar to those of example 1, and the difference between this example and example 1 is that the CeO2-Al2O3CeO in carrier210.0% by weight of the carrier.
Example 6: another limestone-gypsum wet desulfurization catalyst:
this example provides another limestone-gypsum wet desulfurization catalyst, the formulation and preparation method of which are substantially similar to those of example 1, and the difference between this example and example 1 is that the CeO 2-Al2O3CeO in the carrier2Accounting for 15.0 percent of the weight of the carrier.
Example 7: another limestone-gypsum wet desulfurization catalyst:
this example provides another limestone-gypsum wet desulfurization catalyst having a formulation and preparation method substantially similar to those of example 1, and differs from example 1 in that tetranitro aluminum phthalocyanine obtained in step 2.3 is loaded to organic alkali solution-treated CeO instead of tetraamino aluminum phthalocyanine2-Al2O3In a carrier.
Example 8: another limestone-gypsum wet desulfurization catalyst:
this example provides another limestone-gypsum wet desulfurization catalyst, the formulation and preparation method of which are substantially similar to those of example 1, and the difference between this example and example 1 is that tetracarboxylic acid aluminum phthalocyanine is loaded to organic alkali solution-treated CeO instead of tetraamino aluminum phthalocyanine2-Al2O3In a carrier.
Example 9: another limestone-gypsum wet desulfurization catalyst:
this example provides another limestone-gypsum wet desulfurization catalyst, the formulation and preparation method of which are substantially similar to those of example 1, and the difference between this example and example 1 is that AlClPc (NH)2)4/CeO2-Al2O3The catalyst was not modified with lanthanum chloride solution.
Experimental example 2: and (3) desulfurization efficiency detection:
The desulfurization catalysts in examples 1 to 9 were compounded into a finished product, and then added into an absorption tower, after a desulfurization system was operated for 1 hour and 2 hours, the concentration of sulfur dioxide at a smoke outlet was counted, and compared with the desulfurization rate (control group) when the catalyst described in the above example was not added, the statistical results are shown in table 1.
TABLE 1 desulfurization efficiency statistics
Figure 301780DEST_PATH_IMAGE002
It can be seen from table 1 that the catalyst in example 1 of the preferred embodiment of the present application has a desulfurization rate of 99.5% or more, and the desulfurization rate of 99.9% can be achieved after 2 hours, and it does not generate harmful substances such as "aerosol" which block pipes, nozzles and demisters, and has no negative effect on the desulfurization system after long-term use, improves the dehydration rate of gypsum and shortens the dehydration time, and has long action time and small dosage, and reduces energy consumption to a certain extent and improves the quality of byproduct gypsum.
Experimental example 3: and (3) detecting the desulfurization efficiency duration degree:
the desulfurization catalysts of example 1 were each subjected to statistics of their continuous desulfurization effects, and the statistical results are shown in FIG. 4. As can be seen from the graph of FIG. 4, the limestone-gypsum wet desulphurization catalyst in the technical scheme of the invention can complete over 90% of desulphurization effect within 0.5h, and the higher desulphurization effect can continuously last for over 10h, and the catalyst has long action time and small dosage, reduces the production energy consumption to a certain extent and saves the cost.
Conventional techniques in the above embodiments are known to those skilled in the art, and thus will not be described in detail herein.
While the above detailed description has shown, described, and pointed out novel features as applied to various embodiments, it will be understood that various omissions, substitutions, and changes in the form and details of the device or method illustrated may be made without departing from the spirit of the disclosure. In addition, the various features and methods described above may be used independently of one another, or may be combined in various ways. All possible combinations and sub-combinations are intended to fall within the scope of the present disclosure. Many of the embodiments described above include similar components, and thus, these similar components are interchangeable in different embodiments. While the invention has been disclosed in the context of certain embodiments and examples, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments to other alternative embodiments and/or uses and obvious modifications and equivalents thereof. Accordingly, the invention is not intended to be limited by the specific disclosure of preferred embodiments herein.

Claims (4)

1. A limestone-gypsum wet desulphurization catalyst, characterized in that the catalyst comprises a carrier and an active component loaded on the carrier, wherein,
The carrier comprises CeO treated by organic alkali solution2-Al2O3Carrier, CeO2CeO (CeO)2-Al2O30.2-2.0% of the weight of the carrier;
the active component comprises tetraaminochloroaluminum phthalocyanine (AlClPc (NH)2)4) The active component is 4.6-6.6% of tetraaminochloroaluminum phthalocyanine in percentage by weight of the catalyst;
treatment of CeO with organic alkali solution2-Al2O3The carrier comprises the following steps: adding CeO2-Al2O3Soaking the carrier in a solution containing organic alkali, then washing the carrier to be neutral, and drying the carrier for 2 to 5 hours at the temperature of 80 to 120 ℃ to obtain CeO treated by the organic alkali solution2-Al2O3A carrier;
the organic alkali is selected from at least one of ethanolamine, diethanolamine, triethanolamine, glycol amine, methyl ethanolamine or ethylenediamine;
CeO treated with organic alkali solution2-Al2O3The method for loading the active component tetraaminochloroaluminum phthalocyanine on the carrier comprises the following steps:
1) dissolving tetraaminochloroaluminum phthalocyanine in a large amount of DMF at a frequency of 62-70 KHz and a strength of 0.5-0.8 w/cm2The ultrasonic wave is oscillated and dissolved for at least 1h to ensure that the mixture is uniformly dissolved;
2) treating with organic alkali solutionLatter CeO2-Al2O3Roasting the carrier at the temperature of 240-280 ℃ for at least 3h, cooling to room temperature, putting into the mixed solution in the step 1), performing ultrasonic treatment for at least 45min, and performing magnetic stirring for 24 h;
3) filtering the mixed solution obtained in the step 2), taking the filtrate, sequentially washing the filtrate with DMF (dimethyl formamide) and deionized water to be colorless, then washing the filtrate with methanol and ethanol for at least 4 times, and drying the filtrate in vacuum at the temperature of 102-110 ℃ for at least 24 hours to obtain AlClPc (NH) 2)4/CeO2-Al2O3；
The catalyst is modified by lanthanum, and the lanthanum modification method comprises the following steps:
1) dissolving lanthanum chloride in deionized water, and performing ultrasonic oscillation to obtain a lanthanum chloride solution;
2) the prepared AlClPc (NH)2)4/CeO2-Al2O3Dipping the catalyst in a lanthanum chloride solution, magnetically stirring and heating in an oil bath for reaction for at least 5h, evaporating water after centrifugation, and calcining at 125-160 ℃ for at least 2h under vacuum to obtain the catalyst La-AlClPc (NH)2)4/CeO2-Al2O3。
2. The catalyst of claim 1, wherein: CeO in the catalyst2-Al2O3The preparation method of the carrier comprises the following steps: uniformly mixing pseudo-boehmite dry powder, sesbania powder and dilute nitric acid solution containing cerium nitrate, extruding the mixture into strips, drying the strips at 80-120 ℃ for 6-10 h, and roasting the strips at 500-600 ℃ for 3-5 h to obtain CeO2-Al2O3And (3) a carrier.
3. The catalyst of claim 2, wherein: the weight ratio of the cerium nitrate to the dilute nitric acid solution, the pseudo-boehmite dry powder and the sesbania powder is 1 (80-120): 60-100): 1-2.
4. Use of the catalyst of any one of claims 1 to 3 in limestone-gypsum wet desulphurization.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB682078A (en) * 1949-07-04 1952-11-05 John Conrad Arnold An improved manufacture of surface covering sheets
CN1583748A (en) * 2004-06-14 2005-02-23 浙江理工大学 Metalphthalocyanine derivative, salt and preparing method thereof
CN102603258A (en) * 2011-10-11 2012-07-25 可耐福石膏板(芜湖)有限公司 Water-tolerant caulking gypsum powder and preparation method thereof
CN102872718A (en) * 2011-07-11 2013-01-16 中国石油化工股份有限公司 Oxidation method of wet flue gas desulfurizing liquid
CN106582703A (en) * 2016-12-26 2017-04-26 中国石油大学(北京) Gasoline selective hydrodesulfurization catalyst as well as preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB682078A (en) * 1949-07-04 1952-11-05 John Conrad Arnold An improved manufacture of surface covering sheets
CN1583748A (en) * 2004-06-14 2005-02-23 浙江理工大学 Metalphthalocyanine derivative, salt and preparing method thereof
CN102872718A (en) * 2011-07-11 2013-01-16 中国石油化工股份有限公司 Oxidation method of wet flue gas desulfurizing liquid
CN102603258A (en) * 2011-10-11 2012-07-25 可耐福石膏板(芜湖)有限公司 Water-tolerant caulking gypsum powder and preparation method thereof
CN106582703A (en) * 2016-12-26 2017-04-26 中国石油大学(北京) Gasoline selective hydrodesulfurization catalyst as well as preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Graphene wrapped phthalocyanine: Enhanced oxidative desulfurization for dibenzothiophene in fuel;Zhang, Gai，et al.;《APPLIED ORGANOMETALLIC CHEMISTRY》;20180703;第1-8页 *
四氨基酞菁铝的合成及其催化活性研究;薛科创;《当代化工》;20180228;第47卷(第2期);第228-231页 *
石灰石一石膏湿法烟气脱硫工艺原理;李守信等;《华北电力大学学报》;20021031;第29卷(第4期);第91-94页 *

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