CN110589851B - SAPO-34 molecular sieve, copper-based SAPO-34 denitration catalyst, preparation method and application thereof, and denitration method - Google Patents
SAPO-34 molecular sieve, copper-based SAPO-34 denitration catalyst, preparation method and application thereof, and denitration method Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
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Abstract
The invention relates to the field of comprehensive utilization of wastes, and discloses an SAPO-34 molecular sieve and copper-based SAPO-34 denitration catalyst, and a preparation method, application and denitration method thereof. The preparation method of the SAPO-34 molecular sieve comprises the following steps: (1) Mixing the fly ash and a first alkali liquor to carry out a first hydrothermal reaction to obtain a silicon-containing alkali liquor and an aluminum-containing residue; (2) Introducing CO into the silicon-containing alkali liquor 2 To obtain silica gel; (3) Mixing the aluminum-containing residue with a second alkali liquor to perform a second hydrothermal reaction to obtain an aluminum-containing alkali liquor; (4) Introducing CO into the aluminum-containing alkali liquor 2 Gas and pH value are adjusted to obtain alumina; (5) Adding alumina into phosphoric acid solution, mixing with silica gel, adding template agent, aging and hydrothermal crystallizing. The invention fully utilizes the silicon-aluminum resource in the fly ash, can realize industrial production with low energy consumption, and can effectively reduce the content of nitrogen oxides in flue gas by the prepared copper-based SAPO-34 denitration catalyst.
Description
Technical Field
The invention relates to the field of comprehensive utilization of industrial solid wastes, in particular to an SAPO-34 molecular sieve, a preparation method and application thereof, a copper-based SAPO-34 denitration catalyst, a preparation method thereof and a denitration method thereof.
Background
Fly ash is fine ash collected from flue gas generated after coal combustion, and is main solid waste discharged from coal-fired power plants. The main oxide composition of the fly ash of the thermal power plant in China is as follows: siO 2 2 、Al 2 O 3 、FeO、Fe 2 O 3 、 CaO、TiO 2 And so on. Along with the development of the power industry, the discharge amount of fly ash of coal-fired power plants is increased year by year, and the fly ash becomes one of industrial waste residues with larger discharge amount in China. A large amount of fly ash can generate dust without treatment, thereby polluting the atmosphere; if discharged into a water system, the river can be silted, and toxic chemicals in the river can cause harm to human bodies and organisms.
As the chemical components of the fly ash contain various available elements (such as aluminum, silicon and the like), the fly ash is a rich resource with great development value. If the useful substances in the fly ash can be effectively recovered, not only can the circular economy and the saving economy be developed, but also the damage of ore mining to the natural ecological environment can be reduced. The main object of the comprehensive utilization of fly ash is alumina (Al) as the main component 2 O 3 ) And silicon dioxide (SiO) 2 ) Generally, high-alumina fly ash (alumina content is more than 35%) is selected as raw material to be extracted and oxidizedInvestigation of aluminum. The high-alumina fly ash aluminum extraction only aims at the fly ash with the alumina content of more than 35 percent, and the technical route has no universality. The total amount of silicon and aluminum resources in the fly ash accounts for 60-95%, and if the silicon and aluminum resources in the fly ash can be simultaneously utilized, the defects of long and complex technical routes of the step-by-step aluminum and silicon extraction process can be overcome. Therefore, a technical route which can simultaneously utilize the silicon-aluminum resource in the fly ash to prepare a product with higher added value and is suitable for all fly ashes is urgently sought.
Nitrogen oxides (NOx) are one of the main atmospheric pollutants, causing great harm to human bodies, environment and ecology, and effective control and reduction of the emission of the nitrogen oxides are required to improve the quality of the atmospheric environment. Most current NOx control technologies employ Selective Catalytic Reduction (SCR) denitration technologies. The key of the denitration technology is a catalyst, and the catalyst for general commercial use is V 2 O 5 -WO 3 /TiO 2 The optimal active temperature window is higher (300-400 ℃). In order to meet the requirement of the temperature window, a catalytic bed layer is generally arranged in front of a dust remover, and the arrangement method not only can cause sulfur poisoning and dust blockage of the catalyst, but also needs a larger space behind the furnace; v in the active component has toxicity and is not beneficial to ecological environment and body health; in addition, the temperature of flue gas discharged by equipment such as sintering machines and pelletizing machines in steel plants is less than 200 ℃, and the active temperature window of the medium-high temperature SCR catalyst cannot be met, so that the development of the low-temperature SCR technology has very important significance.
In recent years, low-cost and nontoxic molecular sieve catalysts have been favored by researchers because of their advantages of high activity, wide reaction temperature window, appropriate acidity, good stability, and the like. Having NH 3 There are many structures of molecular sieves active in SCR, such as ZSM-5, BEA, USY, SAPO-34, SSZ-13, etc., which are commonly known.
In recent years, fly ash is used as a raw material, and simultaneously, silicon-aluminum resources are efficiently utilized to prepare a silicon-aluminum molecular sieve, which mainly comprises the following steps: a type, X type, Y type, P type, SAPO-34, ZSM-5, beta type and other microporous molecular sieves.
CN103449467A discloses a method for preparing 13X molecular sieve from high-alumina fly ash, which comprises: mixing the high-alumina fly ash with alkali liquor to carry out pre-desiliconization reaction, and filtering to obtain desiliconized solution; mixing the desiliconized solution with white carbon black to obtain modified desiliconized solution; mixing the modified desiliconized solution with an aluminum source to obtain a silicon-aluminum sol; and crystallizing, filtering, washing and drying the silicon-aluminum sol to obtain the 13X molecular sieve. The method synthesizes the 13X molecular sieve aiming at the filtrate obtained after the aluminum is extracted from the high-alumina fly ash under the condition of adding an aluminum source, and does not realize the synchronous utilization of silicon-aluminum resources in the fly ash.
CN104291349A discloses a method for preparing a P-type molecular sieve by using fly ash as a raw material, which comprises: 1. pretreating and activating the fly ash; 2. preparing sodium silicate and sodium metaaluminate by using the activated fly ash; 3. synthesizing a P-type molecular sieve: firstly, uniformly mixing a sodium silicate solution and a sodium salt, then dropwise adding the sodium metaaluminate solution into the mixed solution, and finally adding an organic steric hindrance agent and a proper amount of deionized water to form a reaction mixture, wherein the organic steric hindrance agent M is at least one of ethanolamine, diethanolamine and triethanolamine; putting the mixed materials into a polytetrafluoroethylene container, and stirring for 30min at the speed of 100r/min-300 r/min; then putting the mixture into a stainless steel reaction kettle, and carrying out hydrothermal synthesis for 2-8 h at the temperature of 30-140 ℃; and taking out a product in the reaction kettle, centrifugally separating, washing for 3-4 times by using deionized water, and drying for 12 hours at 120 ℃ to obtain the P-type molecular sieve.
CN103787354A discloses a method for preparing MCM-41 molecular sieve by using fly ash, which comprises: a. drying the fly ash raw powder to constant weight, mixing the fly ash raw powder with HCl solution, stirring, centrifuging, washing and drying for later use; b. b, mixing and calcining the fly ash treated in the step a with NaOH, cooling and grinding into fine powder, adding the obtained ground calcined substance into deionized water, mixing, stirring, and performing centrifugal separation to obtain a supernatant; c. weighing a template CTAB, dissolving in deionized water, continuously stirring under a water bath condition, dropwise adding the supernatant obtained in the step b, adjusting the pH of the solution by using HNO3, continuously stirring to obtain a gelatinous substance, carrying out crystallization reaction on the obtained gelatinous substance, naturally cooling to room temperature after crystallization, centrifuging, washing, drying and roasting to obtain the MCM-41 molecular sieve. The pure silicon molecular sieve obtained by the method does not contain aluminum element and does not realize the synchronous utilization of silicon-aluminum resources.
CN106082267A discloses a method for preparing SAPO-34 molecular sieve from fly ash by microwave hydrothermal coupling, which comprises: 1) Grinding and roasting the fly ash, washing with water, pickling with acid, washing with water, and drying to obtain fly ash microspheres; 2) Measuring the content of alumina and silicon oxide in the fly ash microspheres, mixing the fly ash microspheres, phosphoric acid, a template agent and water in sequence according to the content to form a crystallization stock solution, calculating according to the content of alumina in the fly ash, calculating according to phosphorus pentoxide by using phosphoric acid, wherein the mass ratio range is as follows: phosphorus pentoxide: alumina =1 to 3, templating agent: alumina =2: alumina =90, 1-180, stirring to mix the crystallization stock solution uniformly, wherein the ratio is the mass ratio of the substances; 3) Transferring the uniformly stirred crystallization stock solution into a hydrothermal kettle with tetrafluoroethylene as a lining, and performing microwave hydrothermal coupling crystallization; 4) And cooling the crystallized solution, taking out, washing, centrifuging, filtering, washing and drying the crystallized product, and then roasting to remove the template agent to obtain the SAPO-34 molecular sieve. The method needs to grind and roast the fly ash at high temperature, thus having large energy consumption and non-green process; and the microwave step is adopted, so that the industrial production is difficult to realize.
As can be seen from the existing documents and patent reports, the related research on the preparation of the SAPO-34 molecular sieve by using the fly ash is less, and CN106082267A discloses a method for preparing the SAPO-34 molecular sieve, but the calcination is needed, the energy consumption is higher, and the industrial production is difficult to realize. The denitration catalyst prepared by the prior art does not have good catalytic activity in a medium-low temperature range (less than 300 ℃), and has the defects of short service life, poor high-temperature selectivity, biotoxicity of vanadium and the like.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, a large amount of energy consumption is needed for calcining the fly ash, industrial production is difficult to realize, and a denitration catalyst has poor catalytic activity and poor selectivity in a medium-low temperature range and has biotoxicity, and provides an SAPO-34 molecular sieve and a copper-based SAPO-34 denitration catalyst, and a preparation method, application and a denitration method thereof. The SAPO-34 molecular sieve and copper-based SAPO-34 denitration catalyst prepared by the method not only fully utilizes the silicon-aluminum resource in the fly ash, but also has the advantages of low energy consumption and realization of industrial production. The SAPO-34 molecular sieve prepared by the invention can be used in MTO and MTP processes. The prepared copper-based SAPO-34 denitration catalyst can effectively reduce the content of nitrogen oxides in flue gas in a medium-low temperature range, and has the characteristics of high activity, high selectivity and no biotoxicity.
In order to achieve the above object, the present invention provides, in a first aspect, a method for preparing a SAPO-34 molecular sieve, wherein the method comprises the steps of:
(1) Mixing the fly ash and a first alkali liquor to carry out a first hydrothermal reaction, and filtering to obtain a silicon-containing alkali liquor and an aluminum-containing residue;
(2) Introducing CO into the silicon-containing alkali liquor 2 Performing first carbon decomposition on the gas, and performing first drying to obtain silica gel;
(3) Mixing the aluminum-containing residue with a second alkali liquor to perform a second hydrothermal reaction, and filtering to obtain an aluminum-containing alkali liquor;
(4) Introducing CO into the aluminum-containing alkali liquor 2 Performing second carbon decomposition on the gas, adjusting the pH value of the aluminum-containing alkali liquor, performing second drying to obtain aluminum hydroxide crystals, and performing first calcination to obtain aluminum oxide;
(5) And adding the alumina into a phosphoric acid solution, mixing the alumina with the silica gel, adding a template agent for aging and hydrothermal crystallization, and performing third drying and second calcination to obtain the SAPO-34 molecular sieve.
In a second aspect, the invention provides a SAPO-34 molecular sieve, prepared by the above method, wherein the molecular sieve contains 30 to 50 wt.% of Al, based on the total weight of the molecular sieve 2 O 3 6-14% by weight of SiO 2 And 36-64% by weight of P 2 O 5 。
Preferably, the molecular sieve has a microporous structure with a pore volume of 0.08-0.25cm 3 Per g, the specific surface area is 570-595m 2 The pore diameter is 1.70-2nm.
The third aspect of the invention provides the application of the SAPO-34 molecular sieve in MTO and MTP.
The fourth aspect of the invention provides a preparation method of a copper-based SAPO-34 denitration catalyst, wherein the SAPO-34 molecular sieve is impregnated with a copper-containing solution to carry out transition metal loading, and the copper-based SAPO-34 denitration catalyst is obtained through ethanol rotary evaporation and calcination.
The fifth aspect of the present invention provides a copper-based SAPO-34 denitration catalyst prepared by the method described above, wherein the denitration catalyst contains 25 to 45 wt% of Al, based on the total weight of the denitration catalyst 2 O 3 5-10% by weight of SiO 2 35-70% by weight of P 2 O 5 And 1 to 15 wt% of CuO.
The sixth aspect of the invention provides a denitration method, which comprises the steps of contacting industrial waste gas containing nitrogen oxides and mixed gas containing ammonia gas, oxygen and nitrogen with the copper-based SAPO-34 denitration catalyst at the temperature of 100-350 ℃ to carry out denitration reaction; in the industrial waste gas, the volume concentration of nitrogen oxides calculated by NO is 100-1000ppm, the oxygen content in the mixed gas is 3-5 vol%, and the molar ratio of ammonia gas to the nitrogen oxides calculated by NO in the industrial waste gas is (1-3): 1; the volume space velocity of the total feeding amount of the industrial waste gas and the ammonia gas atmosphere is 3000-150000h -1 。
According to the invention, the SAPO-34 molecular sieve and the copper-based SAPO-34 denitration catalyst are synthesized by utilizing the fly ash, so that silicon elements and aluminum elements in the fly ash can be completely converted into effective components in the molecular sieve, the purposes of recycling solid wastes and increasing the additional value of the fly ash are achieved, and the preparation method is suitable for industrial production.
Compared with the existing denitration catalyst, the copper-based SAPO-34 denitration catalyst prepared by the invention has the advantages of low cost, high acidity, excellent oxidation-reduction performance, high utilization rate of silicon-aluminum resources, high activity, high selectivity, larger specific surface area, good thermal stability, high denitration efficiency, safety and no biotoxicity. At the temperature of 150-350 ℃, ammonia is used as a reducing agent to convert nitrogen oxide into nitrogen, the conversion rate of NOx reaches more than 90 percent, the denitration window is wider,N 2 the selectivity can reach more than 95 percent, and no by-product N is generated 2 And O is generated. The invention can achieve the purpose of treating wastes with wastes and has good economic and social benefits.
Drawings
FIG. 1 is a process flow diagram for the preparation of SAPO-34 molecular sieve in accordance with the invention;
FIG. 2 is a process flow diagram of the present invention for preparing a copper-based SAPO-34 denitration catalyst;
FIG. 3 is an X-ray powder diffraction pattern of a copper-based SAPO-34 denitration catalyst of the present invention;
FIG. 4 is a graph showing N2 adsorption and desorption curves of the copper-based SAPO-34 denitration catalyst of the present invention;
FIG. 5 is a graph of the denitration efficiency of the copper-based SAPO-34 denitration catalyst of the present invention;
FIG. 6 is N of a copper-based SAPO-34 denitration catalyst of the present invention 2 And (4) a selectivity graph.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the invention provides a preparation method of SAPO-34 molecular sieve, the process flow diagram of the preparation method of SAPO-34 molecular sieve of the invention can be shown as figure 1, the method comprises the following steps:
(1) Mixing the fly ash and a first alkali liquor to carry out a first hydrothermal reaction, and filtering to obtain a silicon-containing alkali liquor and an aluminum-containing residue;
(2) Introducing CO into the silicon-containing alkali liquor 2 Performing first carbonization on the gas, and performing first drying to obtain silica gel;
(3) Mixing the aluminum-containing residue with a second alkali liquor to perform a second hydrothermal reaction, and filtering to obtain an aluminum-containing alkali liquor;
(4) Introducing CO into the aluminum-containing alkali liquor 2 Performing second carbon decomposition on the gas, adjusting the pH value of the aluminum-containing alkali liquor, performing second drying to obtain aluminum hydroxide crystals, and performing first calcination to obtain aluminum oxide;
(5) And adding the alumina into a phosphoric acid solution, mixing the alumina with the silica gel, adding a template agent for aging and hydrothermal crystallization, and performing third drying and second calcination to obtain the SAPO-34 molecular sieve.
According to the method of the invention, the fly ash can be solid waste discharged from a coal-fired boiler and contains alumina, silica and optional magnesium oxide, potassium oxide, calcium oxide, titanium dioxide, iron oxide and the like.
According to the method, in the step (1), the feeding weight ratio of the fly ash to the first alkali liquor can be 1: (1.5-3); preferably, the first alkali liquor is sodium hydroxide or potassium hydroxide, and further preferably, the concentration of the first alkali liquor is 5-25mol/L.
According to the method of the present invention, the conditions of the first hydrothermal reaction may include, but are not limited to: the temperature is 80-100 ℃, and the time is 4-6h.
According to the process of the present invention, in the step (2), the catalyst contains CO 2 In the gas of (2), CO 2 Is contained in an amount of 40 to 100% by weight. When CO is present 2 When the concentration of (B) is not 100% by weight, the catalyst contains CO 2 The gas may be CO 2 And N 2 The mixture of (4) is not limited thereto.
According to the method of the present invention, the conditions of the first carbon point may include, but are not limited to: the temperature is 40-80 ℃ and the time is 1-2h.
According to the method of the present invention, the conditions of the first drying may include, but are not limited to: the temperature is 95-110 ℃, and the time is 8-10h.
According to the method of the invention, in the step (3), the feeding weight ratio of the aluminum-containing residue to the second alkali liquor can be 1: (1-3); preferably, the second alkali liquor is a mixed liquor of sodium hydroxide and calcium hydroxide, and further preferably, the concentration of the second alkali liquor is 15-20mol/L, wherein the weight ratio of sodium hydroxide to calcium hydroxide is (20-80): (2-6).
According to the method of the present invention, the conditions of the second hydrothermal reaction may include, but are not limited to: the temperature is 240-280 ℃ and the time is 4-6h.
According to the method of the invention, na is contained in the aluminum-containing alkali liquor 2 The concentration of O is 100-150g/L, al 2 O 3 The concentration of (A) is 100-120g/L.
According to the process of the present invention, in step (4), the pH of the aluminum-containing lye may be adjusted to 10 to 12. The aluminium-containing lye within this pH value is more suitable for obtaining aluminium hydroxide crystals.
According to the method of the present invention, the conditions of the second carbonation may include, but are not limited to: the temperature is 20-50 ℃ and the time is 0.5-2h.
According to the method of the present invention, the conditions of the second drying may include, but are not limited to: the temperature is 95-110 ℃, and the time is 8-10h.
According to the method of the present invention, the conditions of the first calcination may include, but are not limited to: the heating rate is 5-10 ℃/min, the temperature is 800-1200 ℃, and the time is 1-3h.
According to the method of the invention, in the step (5), the feeding ratio of the silicon source, the template agent, the aluminum source, the phosphorus source and the water, namely the molar ratio of the silicon oxide, the template agent, the aluminum oxide, the phosphoric acid and the water in the silica gel is (1.5-2): (8-12): (7-10): (6-8): (40-80). Wherein the water is added during the addition of the phosphoric acid solution, and the water can be deionized water, distilled water and the like.
According to the method of the present invention, the template may be an organic amine template, and further preferably, the template is one or more of triethylamine, tetraethyl amine, tetraethyl ammonium hydroxide and morpholine.
According to the method of the present invention, the aging conditions may include, but are not limited to: the temperature is 20-40 ℃ and the time is 6-10h.
According to the method of the present invention, the conditions of the hydrothermal crystallization may include, but are not limited to: the temperature is 170-230 ℃ and the time is 12-48h.
According to the method of the present invention, the conditions of the third drying may include, but are not limited to: the temperature is 95-110 ℃, and the time is 3-8h.
According to the method of the present invention, the conditions of the second calcination may include, but are not limited to: the heating rate is 5-10 ℃/min, the temperature is 550-650 ℃, and the time is 6-8h.
According to a specific embodiment of the present invention, the preparation method of the SAPO-34 molecular sieve can comprise the following steps:
(1) Mixing the fly ash and a first alkali liquor to perform a first hydrothermal reaction, cooling and filtering to obtain a silicon-containing alkali liquor and an aluminum-containing residue;
(2) Introducing CO into the silicon-containing alkali liquor obtained in the step (1) 2 Performing first carbonation on the gas, fully stirring, filtering, washing and drying to obtain silica gel;
(3) Mixing the aluminum-containing residue obtained in the step (1) with a second alkali liquor to perform a second hydrothermal reaction, cooling, filtering, and taking a supernatant for later use, wherein the supernatant is the aluminum-containing alkali liquor;
(4) Introducing CO into the aluminum-containing alkali liquor obtained in the step (3) 2 And (3) carrying out second carbonation and pH value adjustment, drying to obtain aluminum hydroxide crystals, and carrying out first calcination to obtain aluminum oxide.
(5) Adding the alumina obtained in the step (4) into a phosphoric acid solution by adopting a hydrothermal crystallization method, stirring, adding the silica gel obtained in the step (2) into the solution, adding a template agent, fully stirring, aging, placing in a crystallization kettle for hydrothermal crystallization, filtering, washing with deionized water, drying, calcining and removing the template agent to obtain the SAPO-34 molecular sieve.
In a second aspect, the invention provides a SAPO-34 molecular sieve, prepared by the above method, wherein the molecular sieve contains 30 to 50 wt.% of Al, based on the total weight of the molecular sieve 2 O 3 6-14% by weight of SiO 2 And 36-64% by weight of P 2 O 5 。
In the invention, the molecular sieve has a micropore structure and a pore volume of 0.08-0.25cm 3 Per g, specific surface area of 570-595m 2 The pore diameter is 1.70-2nm.
The third aspect of the invention provides the application of the SAPO-34 molecular sieve in MTO and MTP.
The fourth aspect of the invention provides a preparation method of a copper-based SAPO-34 denitration catalyst, wherein the SAPO-34 molecular sieve is impregnated with a copper-containing solution to carry out transition metal loading, and the copper-based SAPO-34 denitration catalyst is obtained through ethanol rotary evaporation and calcination. The process flow diagram for preparing the copper-based SAPO-34 denitration catalyst can be shown in FIG. 2.
According to the method of the invention, the concentration of the copper-containing solution may be 0.02-0.1mol/L. Preferably, the copper-containing solution is used in an amount of 100-200mL relative to 1g of the SAPO-34 molecular sieve. Further preferably, the conditions of the calcination may include, but are not limited to: the heating rate is 5-10 ℃/min, the temperature is 550-650 ℃, and the time is 6-8h.
The fifth aspect of the present invention provides a copper-based SAPO-34 denitration catalyst prepared by the above method, wherein the denitration catalyst contains 25 to 45 wt% of Al, based on the total weight of the denitration catalyst 2 O 3 5-10% by weight of SiO 2 35-70% by weight of P 2 O 5 And 1 to 15 wt% of CuO.
In the invention, the denitration catalyst has a microporous structure and a pore volume of 0.05-0.2cm 3 Per g, the specific surface area is 450 to 580m 2 G, the aperture is 1-1.8nm.
The sixth aspect of the invention provides a denitration method, which comprises the steps of contacting industrial waste gas containing nitrogen oxides and mixed gas containing ammonia gas, oxygen and nitrogen with the copper-based SAPO-34 denitration catalyst at the temperature of 100-350 ℃ to carry out denitration reaction; in the industrial waste gas, the volume concentration of nitrogen oxides calculated by NO is 100-1000ppm, the oxygen content in the mixed gas is 3-5 vol%, and the molar ratio of ammonia gas to the nitrogen oxides calculated by NO in the industrial waste gas is (1-3): 1; the volume space velocity of the total feeding amount of the industrial waste gas and the ammonia gas atmosphere is 3000-150000h -1 。
The present invention will be described in detail below by way of examples.
In the following examples, the chemical composition of fly ash is shown in Table 1.
TABLE 1
Example 1
Preparation of SAPO-34 molecular sieve
(1) Mixing 100g of fly ash (chemical components are shown in table 1) and a sodium hydroxide solution (concentration is 5 mol/L) in a weight ratio of 1;
(2) Introducing CO into the silicon-containing alkali liquor 2 Gas (CO) of 2 Is 40% by weight, N 2 Concentration of 60 wt%), first carbonization for 2h at 40 ℃, fully stirring, filtering, washing with deionized water, and first drying for 10h at 95 ℃ to obtain silica gel;
(3) Mixing the aluminum-containing residue with a sodium hydroxide solution (with the concentration of 15 mol/L) in a weight ratio of 1 2 O concentration of 100g/L, al 2 O 3 The concentration of (A) is 100g/L;
(4) Introducing CO into the aluminum-containing alkali liquor 2 Performing second carbonization for 2h at 20 ℃, adjusting the pH value of the aluminum-containing alkali liquor to 10, performing second drying for 10h at 95 ℃ to obtain aluminum hydroxide crystals, and heating to 800 ℃ at the temperature rate of 5 ℃/min for performing first calcination for 3h to obtain aluminum oxide;
(5) Adding the alumina into a phosphoric acid solution, mixing with the silica gel, and then adding triethylamine (template), wherein the molar ratio of the silica to the triethylamine to the alumina to the phosphoric acid to the water in the silica gel is 1.5:8:7:6: and 40, stirring for 2 hours, standing and aging at 20 ℃ for 10 hours, pouring the crystallization liquid into a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal crystallization at 170 ℃ under autogenous pressure for 48 hours, filtering, washing with deionized water, carrying out third drying at 95 ℃ for 8 hours, and finally heating to 550 ℃ at a heating rate of 5 ℃/min for second calcination for 8 hours to obtain the SAPO-34 molecular sieve.
Wherein the molecular sieve contains 33.2 weight percent of Al based on the total weight of the SAPO-34 molecular sieve 2 O 3 10.5% by weight of SiO 2 And 56.3% by weight of P 2 O 5 。
The SAPO-34 molecular sieve having a microporous structure and a pore volume of 0.0924cm was observed by a specific surface tester (available from Micromeritics, USA, model ASAP 2020) 3 Per g, specific surface area 580.36m 2 The pore diameter is 1.84nm.
Example 2
Preparation of SAPO-34 molecular sieve
(1) Mixing 100g of fly ash (chemical components are shown in table 1) and a potassium hydroxide solution (the concentration is 25 mol/L) according to a weight ratio of 1:1.5, carrying out a first hydrothermal reaction at 100 ℃ for 4h, cooling, and filtering to obtain a silicon-containing alkali liquor (supernatant) and an aluminum-containing residue;
(2) Introducing CO into the silicon-containing alkali liquor 2 Gas (CO) of 2 In a concentration of 90 wt.%, N 2 Concentration of 10 wt%) at 80 deg.C for 1h, stirring, filtering, washing with deionized water, and drying at 110 deg.C for 8h to obtain silica gel;
(3) Mixing the aluminum-containing residue with a potassium hydroxide solution (with the concentration of 20 mol/L) in a weight ratio of 1 2 O concentration of 150g/L, al 2 O 3 The concentration of (b) is 120g/L;
(4) Introducing CO into the aluminum-containing alkali liquor 2 Performing secondary carbonization for 1.5h at 30 ℃ by using gas, adjusting the pH value of aluminum-containing alkali liquor to 12, performing secondary drying for 8h at 110 ℃ to obtain aluminum hydroxide crystals, and heating to 1200 ℃ at the temperature rate of 10 ℃/min for performing primary calcination for 1h to obtain aluminum oxide;
(5) Adding the alumina into a phosphoric acid solution, mixing with the silica gel, and then adding tetraethyl amine (a template), wherein the molar ratio of the silica to the tetraethyl amine to the alumina to the phosphoric acid to the water in the silica gel is 2:12:10:8:80, stirring for 2 hours, standing and aging for 6 hours at 40 ℃, pouring the crystallization liquid into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal crystallization for 12 hours at 230 ℃ and autogenous pressure, filtering, washing with deionized water, performing third drying for 8 hours at 110 ℃, and finally heating to 650 ℃ at a heating rate of 10 ℃/min for second calcination for 6 hours to obtain the SAPO-34 molecular sieve.
Wherein the molecular sieve contains 45.6 weight percent of Al based on the total weight of the SAPO-34 molecular sieve 2 O 3 12.2% by weight of SiO 2 And 42.2% by weight of P 2 O 5 。
The SAPO-34 molecular sieve having a microporous structure and a pore volume of 0.2033cm, observed as in example 1 3 Per g, specific surface area of 579.81m 2 The pore diameter is 1.84nm.
Example 3
Preparation of copper-based SAPO-34 denitration catalyst
Soaking 1g of SAPO-34 molecular sieve obtained in example 1 in 200mL of copper-containing solution with the concentration of 0.02mol/L, magnetically stirring at 60 ℃ for 24h to carry out transition metal loading, then adding ethanol, stirring and evaporating to dryness, and heating to 550 ℃ at the heating rate of 5 ℃/min to calcine for 8h to obtain the copper-based SAPO-34 denitration catalyst.
Based on the total weight of the copper-based SAPO-34 denitration catalyst, the denitration catalyst contains 30.5 weight percent of Al 2 O 3 9.8% by weight of SiO 2 55.2% by weight of P 2 O 5 And 4.5 wt% CuO.
Observing the copper-based SAPO-34 denitration catalyst through a specific surface tester, wherein the denitration catalyst has a microporous structure and a pore volume of 0.07cm 3 G, specific surface area 564.27m 2 The pore diameter is 1.65nm.
An X-ray powder diffractogram of the copper-based SAPO-34 denitration catalyst shown in figure 3 is obtained by observing through an X-ray powder diffractometer (purchased from Bruke company, germany, with the model number of D8 ADVANCE), and as can be seen from the figure, the copper-based SAPO-34 denitration catalyst prepared by the invention has characteristic peaks of a typical chabazite structure, the peak intensities are similar, and the complete H-SAPO-34 Chabazite (CHA) framework structure is still maintained.
Investigating NH at 100-500 ℃ 3 SCR activity, resulting in a denitration efficiency map of the copper-based SAPO-34 denitration catalyst shown in FIG. 4.
Example 4
And (2) soaking 1g of the SAPO-34 molecular sieve obtained in the example 2 in 100mL of copper-containing solution with the concentration of 0.1mol/L, magnetically stirring at 60 ℃ for 24h to carry out transition metal loading, adding ethanol, stirring, evaporating to dryness, heating to 650 ℃ at the heating rate of 10 ℃/min, and calcining for 6h to obtain the copper-based SAPO-34 denitration catalyst.
Based on the total weight of the copper-based SAPO-34 denitration catalyst, the denitration catalyst contains 40.3 weight percent of Al 2 O 3 9.6% by weight of SiO 2 38.85% by weight of P 2 O 5 And 11.25 wt.% CuO.
The copper-based SAPO-34 denitration catalyst having a microporous structure and a pore volume of 0.1864cm was observed as in example 3 3 Per g, specific surface area 542.17m 2 The pore diameter is 1.66nm.
An X-ray powder diffraction pattern similar to that of FIG. 3 was obtained by observation in the same manner as in example 3.
Following the procedure of example 3, a denitration efficiency map similar to that of fig. 4 was obtained.
Comparative example 1
The process of example 3 was followed except that the copper-containing solution having a concentration of 0.02mol/L was replaced with the iron-containing solution having a concentration of 0.02 mol/L. Obtaining the Fe/SAPO-34 denitration catalyst.
Comparative example 2
The procedure of example 3 was followed except that the copper-containing solution having a concentration of 0.02mol/L was replaced with the manganese-containing solution having a concentration of 0.02 mol/L. Obtaining the Mn/SAPO-34 denitration catalyst.
Test example 1
0.3g of the copper-based SAPO-34 denitration catalyst obtained in example 3 was loaded in a fixed tubular reactor, and simulated flue gas (300ppmNO, 300ppmNH) was introduced 3 ，3.0％O 2 ，N 2 As balance gas), space velocity ratioIs 120000h -1 The denitration efficiency, NO conversion rate and N of the catalyst are measured in the temperature range of 100-350 DEG C 2 The selectivities were calculated by the following methods, respectively:
α NO ＝(C in -C out )/C in
its denitration efficiency and N 2 The selectivity is shown in fig. 5 and 6, respectively. As can be seen from FIGS. 5 and 6, the copper-based SAPO-34 denitration catalyst prepared by the invention has the NOx conversion rate (denitration rate) of over 90 percent at the temperature of between 150 and 350 ℃, and N 2 The selectivity is over 95 percent.
Test example 2
Similar results to those of test example 1 were obtained by following the procedure of test example 1 except that the copper-based SAPO-34 denitration catalyst obtained in example 4 was used.
Test comparative example 1
According to the method of example 1, except for using the Fe/SAPO-34 denitration catalyst obtained in comparative example 1, the Fe/SAPO-34 denitration catalyst has a NOx conversion rate of only 40 to 50% at 100 to 350 ℃, and N is 2 The selectivity is 90-95%.
Test comparative example 2
The procedure of example 1 was followed except that the Mn/SAPO-34 denitration catalyst obtained in comparative example 2 was used, and the Mn/SAPO-34 denitration catalyst had a NOx conversion of 90% or more at 100 to 350 ℃ but N 2 The selectivity is only 50-60%.
The embodiments 1 to 4 show that the fly ash can be fully utilized to synthesize the SAPO-34 molecular sieve and the copper-based SAPO-34 denitration catalyst, the silicon element and the aluminum element in the fly ash are all converted into the effective components in the molecular sieve, the purposes of recycling solid wastes and increasing the additional value of the fly ash are achieved, and the preparation method is suitable for industrial production.
As can be seen from the results of test examples 1-2 and test comparative examples 1-2, the copper-based SAPO-34 prepared by the method of the present invention was denitratedWhen the catalyst is at 100-350 ℃, ammonia is used as a reducing agent to convert nitrogen oxide into nitrogen, the conversion rate of NOx can reach more than 90%, the denitration window is wide, and N is 2 The selectivity can reach more than 95 percent. And the Fe/SAPO-34 denitration catalyst or Mn/SAPO-34 denitration catalyst has low NOx conversion rate or N 2 Low selectivity.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (15)
1. A preparation method of SAPO-34 molecular sieve is characterized by comprising the following steps:
(1) Mixing the fly ash and a first alkali liquor to carry out a first hydrothermal reaction, and filtering to obtain a silicon-containing alkali liquor and an aluminum-containing residue; the feeding weight ratio of the fly ash to the first alkali liquor is 1: (1.5-3); the conditions of the first hydrothermal reaction include: the temperature is 80-100 ℃, and the time is 4-6h;
(2) Introducing CO into the silicon-containing alkali liquor 2 Performing first carbonization on the gas, and performing first drying to obtain silica gel; said CO-containing 2 The first carbon content condition comprises: the temperature is 40-80 ℃, and the time is 1-2h; said CO-containing 2 In the gas of (2), CO 2 The content of (B) is 40-100 wt%;
(3) Mixing the aluminum-containing residue with a second alkali liquor to perform a second hydrothermal reaction, and filtering to obtain an aluminum-containing alkali liquor; the feeding weight ratio of the aluminum-containing residue to the second alkali liquor is 1: (1-3); the conditions of the second hydrothermal reaction include: the temperature is 240-280 ℃, and the time is 4-6h; na in the aluminum-containing alkali liquor 2 The concentration of O is 100-150g/L, al 2 O 3 The concentration of (A) is 100-120g/L;
(4) Introducing CO into the aluminum-containing alkali liquor 2 The gas is subjected to secondary carbon content and adjusted to containThe pH value of the aluminum alkali liquor is subjected to secondary drying to obtain aluminum hydroxide crystals, and primary calcination is carried out to obtain aluminum oxide; the second carbonation condition includes: the temperature is 20-50 ℃ and the time is 0.5-2h; adjusting the pH value of the aluminum-containing alkali liquor to 10-12; the conditions of the first calcination include: the heating rate is 5-10 ℃/min, the temperature is 800-1200 ℃, and the time is 1-3h;
(5) Adding the alumina into a phosphoric acid solution, mixing the alumina with the silica gel, adding a template agent for aging and hydrothermal crystallization, and performing third drying and second calcination to obtain the SAPO-34 molecular sieve; the mol ratio of silicon oxide, template agent, aluminum oxide, phosphoric acid and water in the silica gel is (1.5-2): (8-12): (7-10): (6-8): (40-80); the aging conditions include: the temperature is 20-40 ℃, and the time is 6-10h; the conditions of the hydrothermal crystallization comprise: the temperature is 170-230 ℃, and the time is 12-48h; the conditions of the second calcination include: the heating rate is 5-10 ℃/min, the temperature is 550-650 ℃, and the time is 6-8h.
2. The method of claim 1, wherein the lye is sodium hydroxide or potassium hydroxide; the concentration of the alkali liquor is 5-25mol/L.
3. The method of claim 1, wherein the first drying conditions comprise: the temperature is 95-110 ℃, and the time is 8-10h.
4. The method of claim 1, wherein the second alkali solution is a mixture of sodium hydroxide and calcium hydroxide; the concentration of the second alkali liquor is 15-20mol/L.
5. The method of claim 1, wherein, in step (4), the conditions of the second drying comprise: the temperature is 95-110 ℃, and the time is 8-10h.
6. The method of claim 1, wherein the templating agent is an organic amine templating agent; and/or the presence of a gas in the gas,
the third drying conditions include: the temperature is 95-110 ℃ and the time is 3-8h.
7. The method of claim 6, wherein the templating agent is one or more of triethylamine, tetraethyl amine, tetraethyl ammonium hydroxide, and morpholine.
8. The SAPO-34 molecular sieve prepared by the process of any one of claims 1-7, wherein the molecular sieve comprises 30 to 50 wt.% of Al, based on the total weight of the molecular sieve 2 O 3 6-14% by weight of SiO 2 And 36-64% by weight of P 2 O 5 。
9. The SAPO-34 molecular sieve of claim 8, wherein the molecular sieve has a microporous structure with a pore volume of 0.08-0.25cm 3 Per g, specific surface area of 570-595m 2 The pore diameter is 1.70-2nm.
10. Use of the SAPO-34 molecular sieve of claim 8 or 9 in MTO, MTP.
11. A method for preparing a copper-based SAPO-34 denitration catalyst, wherein the SAPO-34 molecular sieve of claim 8 or 9 is impregnated with a copper-containing solution to carry out transition metal loading, and subjected to rotary evaporation of ethanol and calcination to obtain the copper-based SAPO-34 denitration catalyst.
12. The production method according to claim 11, wherein the concentration of the copper-containing solution is 0.02 to 0.1mol/L; and/or the presence of a gas in the gas,
the dosage of the copper-containing solution is 100-200mL relative to 1g of the SAPO-34 molecular sieve; and/or the presence of a gas in the gas,
the conditions of the calcination include: the heating rate is 5-10 ℃/min, the temperature is 550-650 ℃, and the time is 6-8h.
13. The copper-based SAPO-34 denitration catalyst prepared by the method of claim 11 or 12, wherein the medium weight of the denitration catalyst isOn the basis, the denitration catalyst contains 25-45 wt% of Al 2 O 3 5-10% by weight of SiO 2 35-70% by weight of P 2 O 5 And 1 to 15 wt% of CuO.
14. The copper-based SAPO-34 denitration catalyst of claim 13, wherein the denitration catalyst has a microporous structure with a pore volume of 0.05-0.2cm 3 Per g, the specific surface area is 450 to 580m 2 The pore diameter is 1-1.8nm.
15. A flue gas denitration method, which comprises the steps of contacting industrial waste gas containing nitrogen oxides and mixed gas containing ammonia gas, oxygen and nitrogen with the copper-based SAPO-34 denitration catalyst of claim 13 or 14 at the temperature of 100-350 ℃ to carry out denitration reaction; in the industrial waste gas, the volume concentration of nitrogen oxides calculated by NO is 100-1000ppm, the oxygen content in the mixed gas is 3-5 vol%, and the molar ratio of ammonia gas to the nitrogen oxides calculated by NO in the industrial waste gas is (1-3): 1; the volume space velocity of the total feeding amount of the industrial waste gas and the ammonia gas atmosphere is 3000-150000h -1 。
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