Modified spent fcc catalyst preform and method of making

Abstract

The present application relates to a kind of modified waste FCC catalyst precast components and its preparation method, first, the active component in the waste FCC catalyst after pretreatment is activated by using reducing roasting atmosphere;Second, by supplementing active auxiliary agent and active component precursor in waste FCC catalyst, further improve the activity of waste FCC catalyst, and prepare modified waste FCC catalyst;The modified waste FCC catalyst obtained is combined with waste rock wool, and the modified waste FCC catalyst cementing material is prepared;Mixing, shaping and curing with cement, etc., to prepare modified waste FCC catalyst precast component;The present application improves the activity of waste FCC catalyst by specific activation process, which can maximize the advantages of waste FCC catalyst, improve the performance of precast component product, and improve the quality stability of concrete precast component.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of prefabricated components, in particular to a modified waste FCC catalyst prefabricated component and a preparation method thereof. BACKGROUND

[0002] Fabricated building is a building assembled by prefabricated components on site. Compared with traditional building construction projects, fabricated building can not only shorten the construction period, save time, reduce cost and improve construction efficiency, but also has the advantages of reducing energy consumption, reducing pollution and being green and environmentally friendly. The construction industry has a large carbon reduction space and potential, and fabricated building, as an important means of building industrialization transformation, can effectively reduce construction energy consumption and achieve carbon reduction. However, the existing fabricated building has problems of high construction cost, long construction period and low production rate.

[0003] Fluid catalytic cracking is a major domestic oil refining process, through which heavy feedstock oil can be cracked into liquefied gas, gasoline and diesel and other high-value light oil products by the catalytic cracking (FCC) process. The catalytic cracking (FCC) catalyst, as an indispensable component in the process of crude oil processing, has a decisive influence on the reaction performance of the entire FCC device. Domestic oil refining enterprises produce a large amount of waste FCC catalysts every year. The active components in the waste FCC catalysts are unevenly dispersed, mostly in the form of oxide clusters covering the carrier, thereby reducing the activity of the FCC catalysts.

[0004] The main chemical components of waste FCC catalysts are silicon oxide and aluminum oxide, and also contain metal ions such as calcium, iron and magnesium, as well as negative ions such as sulfate. By the principle of hydration reaction of calcium hydroxide with silicon dioxide and aluminum oxide at a saturated vapor pressure to synthesize calcium silicate hydrate and calcium aluminate, waste FCC catalysts can be used as raw materials in building products. However, due to the low activity and difficulty in handling of waste FCC catalysts, most enterprises still use open-air stacking as the treatment method, which not only has high cost, but also causes environmental pollution by harmful metal components in waste FCC catalysts, which is not conducive to the green development of the oil industry.

[0005] Patent CN110540435A discloses a steam pressure aerated concrete prepared from waste FCC catalyst and a preparation method thereof. The waste FCC catalyst is uniformly mixed with desulfurization gypsum, and wet grinding is performed to form a mixed slurry, thereby removing the passivation layer on the surface of the waste FCC catalyst and improving its activity. However, this method has poor improvement effect on the activity of the waste FCC catalyst, resulting in poor frost resistance and thermal conductivity of the aerated concrete, and further affecting the performance of the prepared prefabricated component. SUMMARY

[0006] The present application aims to overcome the above technical deficiencies, and provide a modified waste FCC catalyst precast component and a preparation method thereof, which solves the technical problem that the existing technology cannot prepare a concrete precast component with good frost resistance and thermal conductivity from waste FCC catalyst.

[0007] To achieve the above technical purposes, the technical scheme provided by the present application is:

[0008] In a first aspect, the present application provides a preparation method of a modified waste FCC catalyst precast component, comprising the following steps: (1) pretreating waste FCC catalyst A to obtain pretreated waste FCC catalyst B; (2) performing calcination treatment on the solid waste FCC catalyst B in a reducing calcination gas to obtain waste FCC catalyst C; (3) uniformly mixing the waste FCC catalyst C after reduction calcination with a solidifying agent and water to obtain a waste FCC catalyst-solidifying agent mixed solution, heating and reacting, and after the reaction is completed, performing cooling, filtering, washing and drying to obtain a modified waste FCC catalyst-solidifying agent composite D; (4) impregnating, drying and supplementing an active component precursor to the modified waste FCC catalyst-solidifying agent composite D, and then performing extrusion molding, sealing and placing at room temperature for 12-24 hours to obtain activated modified waste FCC catalyst E; (5) mixing and drying the modified waste FCC catalyst E with waste rock wool fine powder to prepare modified waste FCC catalyst-rock wool composite pellets; and (6) mixing and processing the obtained modified waste FCC catalyst-rock wool composite pellets, cement, quicklime blocks, desulfurization gypsum, aluminum paste, stones, river sand and water, shaping and curing to prepare the modified waste FCC catalyst precast component.

[0009] In a second aspect, the present application provides a modified waste FCC catalyst precast component prepared by the above preparation method.

[0010] Compared with the prior art, the present application has the following beneficial effects:

[0011] The present application first activates the active components in the pretreated waste FCC catalyst by using a reducing calcination atmosphere; secondly, the activity of the waste FCC catalyst is further improved by supplementing active additives and active component precursors in the waste FCC catalyst to prepare a modified waste FCC catalyst; the obtained modified waste FCC catalyst is combined with waste rock wool fine powder to prepare a modified waste FCC catalyst cementing material, which is mixed with cement and the like, shaped and cured to prepare a modified waste FCC catalyst precast component; the present application improves the activity of the waste FCC catalyst through a specific activation process, maximizes the advantages of the waste FCC catalyst, improves the performance of the precast component product, and has good frost resistance and thermal conductivity, improves the quality stability of the concrete precast component, reduces the cost of prefabricated building engineering, saves non-renewable resources, and promotes the green development of prefabricated buildings. DETAILED DESCRIPTION

[0012] In order to make the purpose, technical scheme and advantages of the present application more clear, the present application is further described in detail below in combination with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and not used to limit the present application.

[0013] The present application aims at the problem that the traditional activation method has poor effect on improving the activity of waste FCC catalyst and the development of prefabricated buildings is limited by technology, and proposes an activation process of waste FCC catalyst and a preparation method of modified waste FCC catalyst prefabricated component. The method uses waste FCC catalyst as cementing material, first uses reducing atmosphere to perform calcination activation treatment on the waste FCC catalyst, then supplements the waste FCC catalyst with activation aids and active component precursors, and modifies the waste FCC catalyst by using external agents, so as to improve the activity of the waste FCC catalyst to the greatest extent. The modified waste FCC catalyst is combined with waste rock wool to prepare a concrete prefabricated component. The modified waste FCC catalyst has better activity, can improve the strength of the prefabricated component product, improve the quality stability of the product, reduce the cost of prefabricated building engineering, save non-renewable resources, and promote the green development of prefabricated buildings.

[0014] The present application is a preparation method of a modified waste FCC catalyst prefabricated component, which aims to improve the utilization rate of waste FCC catalyst, improve the performance of concrete prefabricated component products, and improve the strength of the products, and specifically includes the following steps:

[0015] (1) first pretreat the waste FCC catalyst A to obtain pretreated waste FCC catalyst B;

[0016] (2) perform calcination treatment on the pretreated solid waste FCC catalyst B in a reducing calcination gas to obtain waste FCC catalyst C;

[0017] (3) uniformly mix the waste FCC catalyst C after reduction calcination with a solidifying agent and water to obtain a waste FCC catalyst-solidifying agent mixed solution, perform heating reaction, and after the reaction is completed, perform cooling, filtration, washing and drying to obtain a modified waste FCC catalyst-solidifying agent composite D;

[0018] (4) impregnate, dry and supplement the modified waste FCC catalyst-solidifying agent composite D with active component precursors, then perform extrusion molding, and seal and place at room temperature for 12-24 h to obtain activated modified waste FCC catalyst E;

[0019] (5) use a sample preparation crusher to crush the waste rock wool, and grind it into a waste rock wool powder with a specific surface area of 450-470 m 2kg of waste rock wool fine powder, the modified waste FCC catalyst E is mixed with the waste rock wool fine powder in a certain proportion and dried, and the modified waste FCC catalyst-rock wool composite pellets are obtained by using a pelletizer;

[0020] (6) The modified waste FCC catalyst-rock wool composite pellets obtained in step (5), cement, quicklime, desulfurization gypsum, aluminum paste, stone, river sand, and water are mixed according to a certain proportion, and are shaped and cured to obtain the modified waste FCC catalyst prefabricated component.

[0021] Preferably, in step (1), the pretreatment is to place the waste FCC catalyst A under a temperature condition of 100-200°C, and to perform a hydrothermal reaction with water in a ratio of 2:1, and after 2-5 hours of hydrothermal reaction, to cool to room temperature, to mix with water, and to sequentially perform stirring, filtration, and washing at room temperature, and then to dry in an oven at 120°C to obtain the waste FCC catalyst B; wherein the deionized water is used for washing the modified waste FCC catalyst after the hydrothermal reaction.

[0022] Preferably, in step (2), the reducing roasting gas is a mixed gas of one or more of nitrogen and inert gas and hydrogen in any proportion, further preferably a mixed gas of hydrogen and nitrogen, and more further preferably a mixed gas of hydrogen and nitrogen in a volume ratio of 1:1.

[0023] Preferably, in step (2), the reducing roasting is specifically as follows: the waste FCC catalyst B is subjected to reducing roasting at 1100-1250°C for 0.5-1 hour by using the reducing roasting gas.

[0024] Preferably, in step (3), the solidifying agent is a mixture of vinyl triamine, sepiolite powder, and kaolin, and the mass ratio of the vinyl triamine, the sepiolite powder, and the kaolin is (1-5):(0.5-8):(1-7).

[0025] Preferably, in step (3), the mass ratio of the waste FCC catalyst C and the solidifying agent is 1:(1-10), and the waste FCC catalyst and the solidifying agent are mixed and stirred with water in a water-to-material ratio of 3:1.

[0026] Preferably, in step (3), the waste FCC catalyst C after the reducing roasting is combined with the solidifying agent, the waste FCC catalyst and the solidifying agent are weighed according to a certain proportion, water is added for stirring to obtain a waste FCC catalyst-solidifying agent mixed solution. Secondly, the mixed solution is subjected to ultrasonic dispersion to make it more uniformly dispersed, and is stirred and reacted at 70-100°C for 1-2 hours, and after the reaction is completed, the solution is cooled to room temperature and filtered. The filtered solid is rinsed with anhydrous ethanol and deionized water, and is dried at a temperature of 105-115°C.

[0027] Preferably, in step (4), the activating adjuvant is an acidic titanium-silicon composite sol; the mass ratio of the modified waste FCC catalyst-curing agent composite D and the acidic titanium-silicon composite sol is 1:2-1:6, more preferably 1:3.

[0028] Further preferably, in step (4), the acidic titanium-silicon composite sol is prepared by mixing titanium dioxide and white carbon black (a silicon source), and the acidic solution is one of sulfuric acid, hydrochloric acid or nitric acid.

[0029] Further preferably, in step (4), the acidic titanium-silicon composite sol has a mass ratio of titanium source (calculated as TiO2) to silicon (calculated as SiO2) of 3-1, and a pH value of 1-6.

[0030] Preferably, in step (4), the active component precursor is vanadyl sulfate, and the mass fraction is 1.5-8% of the modified waste FCC catalyst-curing agent composite D.

[0031] Preferably, in step (5), the mixing ratio of the modified waste FCC catalyst E to the waste rock wool fine powder is 4:(1-1.5), and the ratio is too large, the waste catalyst is incorporated too much, affecting the strength; the ratio is too small, the waste catalyst is not enough, affecting the economic benefit. The bulk density of the obtained modified waste FCC catalyst-rock wool composite pellet is 450-500 kg / m 3 .

[0032] Preferably, in step (6), the raw materials are counted according to weight parts, and the modified waste FCC catalyst-rock wool composite pellet is 125-200 parts, cement is 200-275 parts, quicklime is 70-120 parts, desulfurization gypsum is 40-60 parts, aluminum paste is 1.2-1.8 parts, stone is 700-750 parts, river sand is 880-900 parts, and water is 170-175 parts.

[0033] A modified waste FCC catalyst prefabricated component, the components of the modified waste FCC catalyst prefabricated component are:

[0034] The modified waste FCC catalyst-rock wool composite pellet is 125-200 parts, cement is 200-275 parts, quicklime is 70-120 parts, desulfurization gypsum is 40-60 parts, aluminum paste is 1.2-1.8 parts, stone is 700-750 parts, river sand is 880-900 parts, and water is 170-175 parts.

[0035] The modified waste FCC catalyst prepared by the application can be applied to the construction of prefabricated buildings.

[0036] The application aims at maximizing waste FCC catalyst resources, and applies modified waste FCC catalysts in the construction of prefabricated buildings; the waste FCC catalysts are modified by using specific activation methods and means, and combined with waste rock wool to prepare waste FCC catalyst prefabricated components with superior performance.

[0037] Main action mechanism and advantages:

[0038] 1. Pretreatment of waste FCC catalysts: Heavy metal elements are deposited in the structure of waste FCC catalysts, which can cause harm to the human body when applied to building materials. Therefore, the waste FCC catalysts are pretreated by hydrothermal reaction. On the one hand, the hydrothermal reaction can solidify the heavy metal elements in the waste FCC catalysts while retaining the activity and relatively high specific surface area of the waste FCC catalysts; on the other hand, the hydrothermal alkaline environment (alkaline after the waste FCC catalysts are added to water) is conducive to the release of Al elements in the waste FCC catalysts, so that the waste FCC catalysts can better participate in the hydration process and facilitate the generation of C-A-S-H gel, thereby strengthening the performance of the prefabricated components.

[0039] 2. Specific activation process: The waste FCC catalysts themselves have a molecular sieve structure, a small specific surface area, and active components that cannot be uniformly dispersed but are mostly in the form of oxide clusters covering the carrier, thereby reducing the activity of the FCC catalysts. First, the waste FCC catalysts B are placed in a reducing atmosphere for calcination to reduce the active components in the form of oxides; second, the waste FCC catalysts C after reduction calcination are compounded with a solidifying agent to modify the waste FCC catalysts C, and the unique process is used to solidify and modify the waste FCC catalysts, thereby enhancing the solidification reaction capacity of the waste FCC catalysts; active additives and active component precursors are supplemented to the waste FCC catalyst-solidifying agent composite D, so that the waste FCC catalysts can exhibit superior hydration effects in the cementitious material system.

[0040] 3. When the waste FCC catalysts are used to prepare prefabricated components, the inert matrix in the waste FCC catalysts can act as micro-aggregate to enhance the rheological properties of the building materials and make the prefabricated components more regular in shape.

[0041] The application will be further described below in conjunction with specific examples. The following description is only exemplary and does not limit the scope of protection.

[0042] Example 1

[0043] 1. Pretreatment of waste FCC catalysts:

[0044] The waste FCC catalyst A is placed at a temperature of 180°C to carry out a hydrothermal reaction, and after reaction for 3h, it is cooled to room temperature. Then the waste FCC catalyst after hydrothermal reaction and water in a mass ratio of 1:1.5 are mixed, and stirring, filtration, washing, and drying are carried out at room temperature to obtain the pretreated waste FCC catalyst B.

[0045] 2. Modification of the waste FCC catalyst:

[0046] Specifically, the following process flow is included:

[0047] (1) The pretreated waste FCC catalyst B is reduced and calcined using a mixed gas of hydrogen and nitrogen in a volume ratio of 1:1, the calcination temperature is 1200°C, and the calcination time is 45min, to obtain the waste FCC catalyst C.

[0048] (2) The waste FCC catalyst C and a solidifying agent (vinyl triamine, sepiolite powder, and kaolin in a mass ratio of 1:3:6) are weighed in a mass ratio of 1:10, water is added (water to material ratio is 3:1) for stirring, to prepare a waste FCC catalyst-solidifying agent mixed solution. Then the mixed solution is ultrasonically dispersed, and stirred at 90°C for 1.5h. After the reaction is completed, the reaction solution is cooled to room temperature, and then filtered. The filtered solid is washed with anhydrous ethanol and deionized water respectively, and then dried at a temperature of 110°C, to obtain the modified waste FCC catalyst-solidifying agent composite D.

[0049] (3) The modified waste FCC catalyst-solidifying agent composite D is impregnated with an activation aid, acid titanium silicon composite sol, in a mass ratio of 1:3, dried, and compensated with 5% of active component precursor vanadyl sulfate based on the mass of the modified waste FCC catalyst-solidifying agent composite D, and then sealed and placed at room temperature for 18h after extrusion molding. Finally, the activated modified waste FCC catalyst E is obtained.

[0050] 3. Preparation of the modified waste FCC catalyst preformed component:

[0051] Raw materials: ordinary Portland cement: 200 parts, modified waste FCC catalyst E: 100 parts, waste rock wool fine powder: 25 parts, quicklime block: 100 parts, desulfurization gypsum: 50 parts, aluminum paste: 1.5 parts, stone: 700 parts, river sand: 880 parts, and water: 170 parts.

[0052] Preparation method:

[0053] (1) The quicklime block is crushed and ground to lime powder of 200 mesh by a jaw crusher and a dry ball mill, and the river sand is ground into a powder by a wet ball mill, and then prepared into a slurry; the aluminum paste is prepared into a slurry; and the cement is directly poured into a cement tank by a tank truck.

[0054] (2) The waste rock wool is broken and ground into fine powder with a specific surface area of 450-470 m 2 / kg by using a sample preparation crusher. The modified waste FCC catalyst E and the waste rock wool fine powder are mixed in a certain proportion (4:1) and dried, and the modified waste FCC catalyst-rock wool composite pellets are obtained by using a pelletizer.

[0055] (3) The various raw materials are weighed and stirred, poured into a pouring mold vehicle, and after pouring is completed, the bubble is arranged by a bubble arrangement machine, and after arrangement is completed, the mold vehicle is transported to a pre-curing kiln for curing, and when the green body reaches a certain hardness, the mold vehicle is transported to a cutting station for cutting.

[0056] (4) After the pre-curing of the green body is completed, it is sent to the cutting area, and the mold vehicle with the green body is lifted to the cutting trolley by a one-time overturning crane. The green body passes through the cutting machine, the secondary overturning table, and then is placed on the steaming trolley. It is transported to the pre-pot static curing room by the chain conveyor and the pot entry transfer vehicle.

[0057] (5) The green body after static curing is taken out of the steaming pot after high temperature and high pressure steam curing for 11-12 h, and is packed into the warehouse after being pried and packed. After hierarchical stacking and natural curing for 10 days, the finished product is obtained.

[0058] Example 2

[0059] The difference from Example 1 is only that the raw material ratio in the preparation of the modified waste FCC catalyst preformed component is different, and the other steps and conditions are the same as those of Example 1; the specific ratio is as follows:

[0060] 3. Preparation of the modified waste FCC catalyst preformed component:

[0061] Raw materials: ordinary Portland cement: 155 parts, modified waste FCC catalyst E: 140 parts, waste rock wool fine powder: 30 parts, quicklime block: 80 parts, desulfurization gypsum: 42 parts, aluminum paste: 1.5 parts, stone: 700 parts, river sand: 880 parts, and water: 170 parts.

[0062] Example 3

[0063] The difference from Example 1 is only that the raw material ratio in the preparation of the modified waste FCC catalyst preformed component in step 3 is different, and the other steps and conditions are the same as those of Example 1; the specific ratio is as follows:

[0064] 3. Preparation of the modified waste FCC catalyst preformed component:

[0065] Raw materials: ordinary Portland cement: 125 parts, modified waste FCC catalyst E: 160 parts, waste rock wool fine powder: 40 parts, quicklime block: 70 parts, desulfurization gypsum: 33 parts, aluminum paste: 1.5 parts, stone: 700 parts, river sand: 880 parts, and water: 170 parts.

[0066] Comparative Example 1

[0067] The difference from Example 2 is only that the process procedure (2) in step 2 of Example 2, i.e. the solidification modification step, is removed, and other steps and conditions are the same as those of Example 2; specifically as follows:

[0068] 2. Modification of the waste FCC catalyst:

[0069] Specifically including the following process procedure:

[0070] (1) The pretreated waste FCC catalyst is reduced and calcined using a mixed gas of hydrogen and nitrogen with a volume ratio of 1:1, the calcination temperature is 1200℃, and the calcination time is 45 min, to obtain the waste FCC catalyst C.

[0071] (2) The modified waste FCC catalyst C after reduction and calcination is impregnated and dried with an activated auxiliary agent acidic titanium-silicon composite sol at a mass ratio of 1:3, 5% of the active component precursor vanadyl sulfate is compensated according to the mass of the modified waste FCC catalyst C, and after extrusion molding, the activated modified waste FCC catalyst E is obtained by sealing and placing at room temperature for 18 h.

[0072] 3. Preparation of the modified waste FCC catalyst preformed member:

[0073] Raw materials: ordinary Portland cement: 155 parts, modified waste FCC catalyst E: 140 parts, waste rock wool fine powder: 30 parts, quicklime block: 80 parts, desulfurization gypsum: 42 parts, aluminum paste: 1.5 parts, stone: 700 parts, river sand: 880 parts, and water: 170 parts.

[0074] Comparative Example 2

[0075] The difference from Example 2 is only that the process procedure (3) in step 2 of Example 2, i.e. the activation step, is removed, and other steps and conditions are the same as those of Example 2; specifically as follows:

[0076] 2. Modification of the waste FCC catalyst:

[0077] Specifically including the following process procedure:

[0078] (1) The pretreated waste FCC catalyst is reduced and calcined using a mixed gas of hydrogen and nitrogen with a volume ratio of 1:1, the calcination temperature is 1200℃, and the calcination time is 45 min, to obtain the waste FCC catalyst C.

[0079] (2) The waste FCC catalyst C and solidifying agent (vinyl triamine, sepiolite powder and kaolin with a mass ratio of 1:3:6) were weighed according to a mass ratio of 1:10, water was added (water material ratio was 3:1) for stirring to prepare a waste FCC catalyst-solidifying agent mixed solution. Then the mixed solution was subjected to ultrasonic dispersion and stirring reaction at 90°C for 1.5h. After the reaction was completed, the reaction solution was cooled to room temperature and then filtered. The filtered solid was washed with anhydrous ethanol and deionized water respectively and then dried at a temperature of 110°C to prepare a modified waste FCC catalyst-solidifying agent composite D.

[0080] 3. Preparation of modified waste FCC catalyst preformed component:

[0081] Raw materials: ordinary Portland cement: 155 parts, modified waste FCC catalyst D: 140 parts, waste rock wool fine powder: 30 parts, quicklime block: 80 parts, desulfurization gypsum: 42 parts, aluminum paste: 1.5 parts, stone: 700 parts, river sand: 880 parts, and water: 170 parts.

[0082] Comparative Example 3

[0083] The difference from Example 2 is that the process flow (3) in step 2 of Example 2 is performed first, and then the process flow (2) in step 2 of Example 2 is performed, that is, the step of impregnating the activation aid is performed first, and then the step of compounding with the solidifying agent is performed, and the other steps and conditions are the same as those of Example 2; specifically as follows:

[0084] 2. Modification of waste FCC catalyst:

[0085] Specifically including the following process flow:

[0086] (1) The pretreated waste FCC catalyst was subjected to reduction roasting using a mixed gas of hydrogen and nitrogen with a volume ratio of 1:1, the roasting temperature was 1200°C, and the roasting time was 45 min to obtain waste FCC catalyst C.

[0087] (2) The modified waste FCC catalyst C and the activation aid acidic titanium silicon composite sol were impregnated and dried according to a mass ratio of 1:3, the active component vanadyl sulfate was supplemented by 5% of the mass of the modified waste FCC catalyst C, and then the mixture was subjected to extrusion molding procedure and sealed at room temperature for 18h. Finally, the activated modified waste FCC catalyst D was prepared.

[0088] (3) The waste FCC catalyst D and the solidifying agent (vinyl triamine, sepiolite powder and kaolin in a mass ratio of 1:3:6) were weighed according to a mass ratio of 1:10, water was added (water material ratio of 3:1) for stirring to prepare a waste FCC catalyst-solidifying agent mixed solution. Then the mixed solution was subjected to ultrasonic dispersion and stirring reaction at 90°C for 1.5h. After the reaction was completed, the reaction solution was cooled to room temperature and then filtered. The filtered solid was washed with anhydrous ethanol and deionized water respectively and then dried at a temperature of 110°C to prepare a modified waste FCC catalyst E.

[0089] 3. Preparation of the modified waste FCC catalyst preformed component:

[0090] Raw materials: ordinary Portland cement: 155 parts, modified waste FCC catalyst E: 140 parts, waste rock wool fine powder: 40 parts, quicklime block: 80 parts, desulfurization gypsum: 42 parts, aluminum paste: 1.5 parts, stone: 700 parts, river sand: 880 parts, water: 170 parts.

[0091] Comparative Example 4

[0092] The difference from Example 2 is only that the waste FCC catalyst is not subjected to any modification treatment, but only subjected to a composite treatment with rock wool. Specifically as follows:

[0093] Preparation of the modified waste FCC catalyst preformed component:

[0094] Raw materials: ordinary Portland cement: 155 parts, waste FCC catalyst: 140 parts, waste rock wool fine powder: 30 parts, quicklime block: 80 parts, desulfurization gypsum: 42 parts, aluminum paste: 1.5 parts, stone: 700 parts, river sand: 880 parts, water: 170 parts.

[0095] (1) The quicklime block was crushed and ground to lime powder of 200 mesh by a jaw crusher and a dry ball mill, and the river sand was ground into powder by a wet ball mill to prepare a slurry; the aluminum paste was prepared into a slurry; the cement was directly poured into a cement tank by a tank truck.

[0096] (2) The waste rock wool was crushed and ground into fine powder with a specific surface area of 450-470 m 2 / kg by a sample preparation crusher, and the waste FCC catalyst was mixed with the waste rock wool fine powder according to a certain ratio (4:1) and dried to obtain waste FCC catalyst-rock wool composite pellets by a pelletizer;

[0097] (3) The various raw materials were weighed and stirred, poured into a pouring mold vehicle, and after pouring was completed, the bubble was arranged by a bubble arrangement machine, and after arrangement was completed, the mold vehicle was transported to a pre-curing kiln for curing, and when the green body reached a certain hardness, the mold vehicle was transported to a cutting station for cutting.

[0098] (4) After the end of the pre-rearing of the blank, it is sent to the cutting area, the mold vehicle with the blank is lifted to the cutting trolley by the one-time overturning crane, the blank passes through the cutting machine, the secondary overturning table, and then is placed on the steaming trolley, and is transported to the pre-pot static room through the chain conveyor and the pot entry transfer vehicle.

[0099] (5) The blank after the end of the static maintenance is taken out of the steaming pot after high-temperature and high-pressure steam maintenance for 11-12h, is pried and packed into the warehouse, is stacked in stages, and is naturally maintained for 10 days to obtain the finished product.

[0100] Performance test

[0101] The prefabricated component prepared by the embodiment of the present application has neat structure, smooth surface, and few problems such as broken corners and broken blocks.

[0102] The modified waste FCC catalyst prefabricated component obtained according to the above mixing ratio and process is subjected to performance test according to the standard "Autoclaved Aerated Concrete Board" (Q / JB HBCL004-2019), and the results are shown in Table 1 as follows:

[0103] Table 1 Working performance of modified waste FCC catalyst prefabricated component after natural maintenance

[0104]

[0105] As shown in Table 1, the prefabricated components prepared from the activated and modified waste FCC catalysts in Examples 1-3 have obviously better performance than the prefabricated components obtained in the national standard and Comparative Examples 1-4. The hydration reaction of silicon and aluminum elements in the waste FCC catalyst synthesizes calcium silicate hydrate and calcium aluminate hydrate, which can improve the strength of the product. The addition of quicklime makes the waste FCC catalyst in a hydrothermal alkaline environment, which is conducive to the release of Al element in the waste FCC catalyst, so that the waste FCC catalyst participates more in the hydration process, which is beneficial to the generation of N-A-S-H gel, improves the bonding force between the internal structures of the product, and further improves the performance of the product. Moreover, the waste rock wool fiber has a small thermal conductivity, and its incorporation can reduce the overall thermal conductivity of the product, improve the thermal insulation performance of the prefabricated component, and reduce the drying shrinkage value of the product. The compressive strength of the prefabricated component obtained by the present application can reach 4.8-5.5MPa, the thermal conductivity is 0.08-0.13W / (m,K), the anti-freezing mass loss is 0.50-0.85%, the strength after freezing can still reach 2.97-3.32MPa, the drying shrinkage is 0.21-0.23mm / m, the performance is stable, and the effect is more prominent when applied to thermal insulation wall materials.

[0106] In addition, the difference in performance between Example 2 and Comparative Example 1 shows that the impregnation of the activation aid and the incorporation of the active component precursor improve the activity of the waste FCC catalyst. The activation aid and the active component precursor, on the one hand, reduce the active component in the waste FCC catalyst, and on the other hand, directly increase the active component in the waste FCC catalyst, both of which work together to enhance the performance of the modified waste FCC catalyst preform. By comparing the performance differences between Example 2 and Comparative Examples 1-4, the combination of the curing agent and the waste FCC catalyst can increase the curing reaction in the preform structure, thereby improving the performance of the preform.

[0107] Compared with the prior art, the present application provides a modified waste FCC catalyst preform and a preparation method thereof, comprising the following steps: first, activating the active component in the pretreated waste FCC catalyst by using a reducing calcination atmosphere; second, further improving the activity of the waste FCC catalyst by supplementing the active aid and the active component precursor in the waste FCC catalyst to obtain a modified waste FCC catalyst; combining the obtained modified waste FCC catalyst with waste rock wool to obtain a modified waste FCC catalyst cementitious material. Finally, the modified waste FCC catalyst cementitious material, cement, quicklime block, desulfurization gypsum, aluminum paste, river sand and stone are mixed and treated according to weight parts, shaped and cured to obtain a modified waste FCC catalyst preform. The present application improves the activity of the waste FCC catalyst through a specific activation process, maximizes the advantages of the waste FCC catalyst, and obtains a concrete preform with excellent and stable working performance, reduces the preparation cost of the concrete preform, and meets the development trend of prefabricated buildings.

[0108] The specific embodiments of the application described above do not constitute a limitation on the scope of protection of the application. Any various other corresponding changes and modifications made in accordance with the technical concept of the application should be included within the scope of protection of the claims of the application.

Claims

1. A process for the preparation of a modified spent FCC catalyst preform, characterized in that, The method comprises the following steps: (1) pretreating the waste FCC catalyst A by a hydrothermal reaction to obtain a pretreated waste FCC catalyst B; (2) calcining the solid waste FCC catalyst B in a reducing calcination gas to obtain a waste FCC catalyst C; (3) uniformly mixing the waste FCC catalyst C after reduction calcination with a solidifying agent and water to obtain a waste FCC catalyst-solidifying agent mixture, heating and reacting, and after the reaction, cooling, filtering, washing and drying to obtain a modified waste FCC catalyst-solidifying agent composite D; the solidifying agent is a mixture of vinyl triamine, sepiolite powder and kaolin in a mass ratio of (1-5):(0.5-8):(1-7); (4) impregnating, drying and supplementing an active component precursor to the modified waste FCC catalyst-solidifying agent composite D, and then extruding to obtain an activated modified waste FCC catalyst E after sealing for 12-24 hours at room temperature; the active component precursor comprises vanadyl sulfate, and the amount of the active component precursor is 1.5-8% of the mass of the modified waste FCC catalyst-solidifying agent composite D; (5) mixing and drying the modified waste FCC catalyst E with waste rock wool powder to obtain modified waste FCC catalyst-rock wool composite pellets; (6) mixing and processing the modified waste FCC catalyst-rock wool composite pellets, cement, quicklime, desulfurization gypsum, aluminum paste, stone, river sand and water to obtain a modified waste FCC catalyst prefabricated component.

2. The method of making a modified spent FCC catalyst preform according to claim 1, characterized in that, In step (1), the pretreatment is to mix the waste FCC catalyst A with water, and then perform a hydrothermal reaction at a temperature of 100-200 ℃, cool to room temperature after the hydrothermal reaction for 2-5 hours, and then perform filtering, washing and drying to obtain the waste FCC catalyst B.

3. The method of making a modified spent FCC catalyst preform according to claim 1, wherein, In step (2), the reducing calcination gas is a mixed gas of one or more of nitrogen and inert gas and hydrogen in any proportion.

4. The method of making a modified spent FCC catalyst preform according to claim 1, characterized in that, In step (2), the waste FCC catalyst B is reduced and calcined in the reducing calcination gas at 1100-1250 ℃ for 0.5-1 hour.

5. The method of making a modified spent FCC catalyst preform according to claim 1, wherein, In step (3), the mass ratio of the waste FCC catalyst C to the solidifying agent is 1:(1-10).

6. The method of making a modified spent FCC catalyst preform according to claim 1, wherein, In step (4), the mass ratio of the modified waste FCC catalyst-solidifying agent composite D to the acidic titanium-silicon composite sol is 1:(2-6).

7. The method of making a modified spent FCC catalyst preform according to Claim 1, characterized by, In step (5), the mixing ratio of the modified waste FCC catalyst E to the waste rock wool powder is 4:(1-1.5).

8. The method of making a modified spent FCC catalyst preform according to claim 1, wherein, In step (6), the raw materials include the modified waste FCC catalyst-rock wool composite pellets 125-200 parts, cement 200-275 parts, quicklime 70-120 parts, desulfurization gypsum 40-60 parts, aluminum paste 1.2-1.8 parts, stone 700-750 parts, river sand 880-900 parts, and water 170-175 parts.

9. The modified waste FCC catalyst prefabricated component prepared by the method according to any one of claims 1-8.

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