Preparation method of catalyst master batch and catalyst master batch thereof

Abstract

The invention belongs to the field of environment-friendly resource recycling, particularly relates to a preparation method of a catalyst master batch and the catalyst master batch thereof, and more particularly relates to a preparation method of the catalyst master batch using an FCC waste catalyst and the catalyst master batch prepared by using the method. By using the method disclosed by the invention, the two industrial solid wastes, namely the FCC waste catalyst and the fly ash, can be subjected to resource utilization, the preparation process is simple, a complicated pretreatment process is not needed, the prepared catalyst master batch is high in strength, good in acid resistance, high in additional value and low in stacking density, the filling amount of a reactor can be increased, and the production cost is reduced. And the catalytic efficiency per unit volume is obviously improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of environmental protection and resource recycling, and particularly relates to a preparation method of a catalyst master batch, and a catalyst master batch thereof, and more particularly relates to a preparation method of a catalyst master batch using FCC waste catalyst, and a catalyst master batch prepared by using the method. BACKGROUND

[0002] Fluid Catalytic Cracking (FCC) process plays an important role in the petroleum refining (refining) industry, and the FCC catalyst plays an important role in the process. Because the crude oil mined usually contains a large amount of heavy metals, in the refining process, the heavy metals in the crude oil will gradually deposit on the FCC catalyst, resulting in reduced catalyst activity, poor product selectivity, and even collapse of the molecular sieve structure, and complete deactivation of the catalyst.

[0003] The waste FCC catalyst has heavy metal elements deposited thereon, and the waste FCC catalyst was listed in the newly published "National Hazardous Waste List" in 2016. At present, there is no good method and way for the treatment and utilization of such a large amount of FCC waste catalyst. The main commonly used treatment method is landfill as solid waste, which not only wastes a large amount of resources, but also may pollute the environment if not properly treated due to the presence of a certain amount of heavy metals such as nickel and vanadium in the waste catalyst. The current researches mostly use it as fine aggregate or filler for cement or asphalt, and the value of the finished product is still low.

[0004] Therefore, there is a need in the art for a method that can recycle FCC waste catalyst and at the same time generate a product with high added value. SUMMARY

[0005] The FCC catalyst is composed of zeolite (molecular sieve), which is a crystalline silicate with a crystal structure, with SiO2 and Al2O3 as main components, has a large specific surface area and pore volume, and the used FCC waste catalyst generally also contains 10% to 25% by mass of zeolite. Although it has lost catalytic activity, its internal structure has not been completely destroyed and still has certain utilization value. Therefore, its use for making catalyst master batch is a new idea.

[0006] Therefore, in a first aspect, the present application provides a preparation method of a catalyst master batch, comprising the following steps:

[0007] Step S1: mixing the FCC waste catalyst with white cement, fly ash floating bead, vermiculite clay, kaolin, calcium-based bentonite, and glass floating bead to prepare a mixture;

[0008] Step S2: preparing catalyst master granule precursor by rolling granulation using the mixture in step S1; and

[0009] Step S3: curing and drying the catalyst master granule precursor prepared in step S2, to finally prepare catalyst master granule.

[0010] Using the method of the present application, both FCC waste catalyst and fly ash, two kinds of industrial solid waste, can be resourceized, and the preparation process is simple without complex pretreatment process. The catalyst master granule prepared has high strength, good acid resistance, and high added value, and at the same time has low bulk density, which can increase the reactor loading and significantly improve the catalytic efficiency per unit volume.

[0011] In some specific embodiments, in step S1, the mass ratio of FCC waste catalyst, white cement, fly ash floating bead, vermiculite clay, kaolin, calcium-based bentonite, and glass floating bead is (15-25):(25-35):(10-20):(15-20):(5-15):(5-15):(10-20).

[0012] In some specific embodiments, in step S1, the particle size of the glass floating bead is 200-300 mesh, and the bulk density is 0.15-0.3 g / ml.

[0013] In some specific embodiments, in step S1, the particle size of the white cement, fly ash floating bead, vermiculite clay, kaolin, and calcium-based bentonite is 500-4000 mesh.

[0014] In some specific embodiments, in step S2, the particle size of the catalyst master granule precursor is 1.5-2.5 mm, and optionally 2 mm.

[0015] In some specific embodiments, in step S2, the mixture in step S1 is bonded into a catalyst master granule precursor by a binder.

[0016] Further, the mass ratio of the binder to the mixture is (8-10):(5-7).

[0017] Still further, the binder is polyvinyl alcohol.

[0018] In some specific embodiments, in step S2, the parameters of rolling granulation are a rotation speed of 40-150 r / min and / or a granulation time of 80-120 min.

[0019] In some specific embodiments, in step S3, before curing, natural air drying is further included. Still further, the time of natural air drying is 24-36 h.

[0020] In some specific implementations, in step S3, the maintenance is water spraying maintenance.

[0021] Furthermore, the amount of water sprayed for the water curing is 10-15% of the mass of the catalyst masterbatch precursor.

[0022] Furthermore, after water spraying, the product is allowed to air dry naturally. Even further, the natural air drying time is 24–36 hours.

[0023] Furthermore, the number of times for water spraying maintenance is 2 to 4.

[0024] In some specific implementations, the drying parameters in step S3 are: temperature of 35-45°C and / or duration of 12-18 hours.

[0025] In some specific embodiments, the bulk density of the catalyst masterbatch is 0.40 to 0.45 g / mL.

[0026] In some specific embodiments, the catalyst masterbatch also satisfies at least one of the following conditions:

[0027] The particle size is 1.5mm to 2.5mm;

[0028] The compressive strength is 125-150 N / particle;

[0029] Wear rate <1%; or

[0030] The total amount of metal leached is less than 0.05 mg / kg.

[0031] Secondly, the present invention provides a catalyst masterbatch, which is prepared by the preparation method described above.

[0032] In some specific embodiments, the bulk density of the catalyst masterbatch is 0.40 to 0.45 g / mL.

[0033] In some specific embodiments, the catalyst masterbatch also satisfies at least one of the following conditions:

[0034] The particle size is 1.5mm to 2.5mm;

[0035] The compressive strength is 125-150 N / particle;

[0036] Wear rate <1%; or

[0037] The total amount of metal leached is less than 0.05 mg / kg.

[0038] Thirdly, the present invention provides an application of catalyst masterbatch for the preparation of catalysts.

[0039] Furthermore, the catalyst is a heterogeneous catalyst. Attached Figure Description

[0040] Figure 1 The catalyst masterbatch prepared in one embodiment of this application. Detailed Implementation

[0041] The present invention will be described in detail below with reference to specific implementation schemes and embodiments, thereby making the advantages and various effects of the present invention more clearly apparent. Those skilled in the art should understand that these specific implementation schemes and embodiments are for illustrative purposes only and are not intended to limit the present invention.

[0042] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0043] Unless otherwise specified, all embodiments and optional embodiments of this application may be combined to form new technical solutions.

[0044] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0045] If not otherwise specified, all steps of the present application can be performed in sequence or randomly, preferably in sequence. For example, the method comprising steps (a) and (b) means that the method can comprise steps (a) and (b) in sequence, or steps (b) and (a) in sequence. For example, the method comprising step (c) means that step (c) can be added to the method in any sequence, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0046] If not otherwise specified, the terms used in the present application have the commonly understood meaning by the person skilled in the art.

[0047] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and / or "comprising", when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. As used herein the term "and / or" includes any and all combinations of associated items.

[0048] The present application improves the formula, reduces the density of the master batch, and reduces the overall bulk density of the catalyst during preparation. The reduced bulk density of the catalyst has obvious advantages, such as better contact effect of the floating catalyst during operation, higher catalytic efficiency, less fouling, lower backwashing frequency to save energy consumption, lower wear rate, lower transportation cost, etc.

[0049] The addition of fly ash floating beads and glass floating beads, which are two kinds of super-light powders, reduces the weight of the master batch. However, the light weight of the powders makes it difficult to compress them tightly during granulation, resulting in a decrease in strength. The adhesion of fly ash floating beads and glass floating beads is also poor. In order to achieve light weight while ensuring the strength of the master batch, more white cement is added to the formula of the light weight master batch, as white cement is the source of strength of the sinter-free particles. In addition, vermiculite clay, which has higher adhesion, is added.

[0050] The term "strength" refers to the ratio of the remaining weight of the material to the original weight under specific shock or scouring conditions, which can also be expressed as the wear rate, and the relationship is 1-strength=wear rate.

[0051] The term "Guangxi white clay" is a kind of soft kaolin produced in Weilupo area of Fusui County, Guangxi, and its main components are disordered kaolinite (70%~95%), quartz (<30%) and trace titanium iron minerals.

[0052] The term "calcium-based bentonite" refers to a natural clay mineral with calcium montmorillonite (Ca-Montmorillonite) as the main component, and its interlayer cation is mainly calcium ion (Ca 2+ ) as the main component.

[0053] The term "fly ash floating bead" refers to the part of ordinary fly ash with a density less than water, and its density is generally 0.5~0.6 g / mL, while the density of ordinary fly ash is between 1.07~2.4 g / mL. The density of fly ash floating bead is lighter, and the content of silicon dioxide is higher.

[0054] The term "glass floating bead" refers to a kind of hollow, wall-thick and spherical glass particles, and its main component is borosilicate with a particle size of 44~74 μm and a bulk density of 0.15~0.3 g / ml.

[0055] Example 1, preparation of catalyst master batch

[0056] Step S1: The FCC spent catalyst from petrochemical companies such as Maoming, Changling, etc. does not need any pretreatment, and the FCC and white cement, fly ash floating bead, Guangxi white clay, kaolin, calcium-based bentonite and glass floating bead are mixed uniformly according to the ratio of 15:30:15:15:5:10:10.

[0057] Step S2: The mixed powder is prepared into spherical particles with a particle size of about 2 mm by rolling granulation with polyvinyl alcohol as the binder. The rolling granulation speed is 140 r / min, the rolling granulation time is 90 min, the powder-water weight ratio is 9:5, and the catalyst master batch precursor is prepared.

[0058] Step S3: After the rolling granulation of the catalyst, the catalyst is naturally air-dried for 30 h, and then the first water spraying is carried out, and the spraying amount is 15% of the total weight of the catalyst master batch precursor. After spraying, the catalyst is naturally air-dried for 30 h, and the curing is carried out for 3 times. After the curing is completed, the catalyst master batch precursor is placed in an oven for complete drying, and the oven temperature is 35℃, and the drying time is 15 h. The catalyst master batch is prepared, as shown in Figure 1 .

[0059] Example 2

[0060] Example 1 is repeated, and the difference is only that the mixing ratio of each component in step S1 is 20:25:15:15:5:5:15.

[0061] Comparative Example 1

[0062] Example 1 was repeated, except that in step S1, white cement was replaced with 1:1 fly ash and silica powder.

[0063] Comparative Example 2

[0064] Example 1 was repeated, except that in step S1, calcium-based bentonite was replaced with sodium-based bentonite.

[0065] Properties of the catalyst master batch

[0066] The catalyst master batch prepared in Examples 1 to 2 and Comparative Examples 1 to 2 was used to test the properties of the catalyst master batch, and the results are shown in Table 1.

[0067] Table 1

[0068]

[0069] It should be noted that the present application is not limited to the above-described embodiments. The above-described embodiments are merely examples, and embodiments having substantially the same configuration and exerting the same effects as the technical idea within the scope of the technical solution of the present application are all included in the technical scope of the present application. Furthermore, within the scope of the gist of the present application, other modes obtained by applying various modifications to the embodiments, or by combining part of the configuration elements of the embodiments, are also included in the scope of the present application.

Claims

1. A method for preparing a catalyst masterbatch, comprising the following steps: Step S1: Mix the FCC waste catalyst with white cement, fly ash cenospheres, Vero ball clay, kaolin, calcium-based bentonite, and glass cenospheres to prepare a mixture; Step S2: Using the mixture from step S1, prepare a catalyst masterbatch precursor by rolling granulation; and Step S3: The catalyst masterbatch precursor prepared in step S2 is cured and dried to finally obtain the catalyst masterbatch.

2. The preparation method according to claim 1, characterized in that, In step S1, the mass ratio of FCC waste catalyst to white cement, fly ash cenospheres, Vero ball clay, kaolin, calcium-based bentonite, and glass cenospheres is (15-25):(25-35):(10-20):(15-20):(5-15):(5-15):(10-20).

3. The preparation method according to claim 1, characterized in that, In step S2, the mixture from step S1 is bonded together with a binder to form a catalyst masterbatch precursor.

4. The preparation method according to claim 3, characterized in that, The mass ratio of the adhesive to the mixture is (8-10):(5-7).

5. The preparation method according to claim 1, characterized in that, In step S2, the parameters for rolling granulation are a rotation speed of 40–150 r / min and / or a granulation time of 80–120 min.

6. The preparation method according to claim 1, characterized in that, In step S3, the curing is water spraying curing, wherein the amount of water sprayed during water spraying curing is 10-15% of the mass of the catalyst masterbatch precursor.

7. A catalyst masterbatch, prepared by the preparation method according to any one of claims 1 to 6.

8. The catalyst masterbatch according to claim 7, characterized in that, The bulk density of the catalyst masterbatch is 0.40–0.45 g / mL.

9. The catalyst masterbatch according to claim 8, characterized in that, The catalyst masterbatch also satisfies at least one of the following conditions: The particle size is 1.5mm to 2.5mm; The compressive strength is 125-150 N / particle; Wear rate <1%; or The total amount of metal leached is less than 0.05 mg / kg.

10. The application of the catalyst masterbatch according to any one of claims 7 to 9 in the preparation of catalysts.

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