CN115945226A - Pulping and mixing process - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention provides a pulping and mixing process, which comprises the following steps: forming at least one of the slurries to be mixed into a colloidal slurry through a gelling reaction; mixing the colloidal slurry with other slurry to be mixed to obtain blended slurry; and (3) mixing the blending slurry by an ultrasonic dispersion-colloid mill for a plurality of times of circulating treatment until the particle size in the blending slurry is in single distribution and the change rate of the particle size along with the circulating treatment is less than 10%. The invention combines the advantages of gelatinization, ultrasonic dispersion and colloid mill mixing, and carries out circulating treatment, thereby being beneficial to realizing the dispersion and combination of nano-scale particles of different slurry and preventing the segregation and aggregation of different combinations, particularly carrier components. Before being applied to copper-zinc binary precursor slurry and aluminum carrier in the preparation process of methanol synthesis catalystMixing of precursor slurry, prepared catalyst Cu/ZnO active center and Al 2 O 3 The carrier components are uniformly distributed in a nanoscale, so that the migration and agglomeration of active center components are prevented, and the stability of the catalyst is improved.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a pulping and mixing process, in particular to a pulping and mixing process of copper-zinc binary precursor slurry and aluminum carrier precursor slurry of a methanol synthesis catalyst.
Background
Cu/ZnO/Al 2 O 3 The catalyst is a methanol synthesis catalyst with excellent performance and occupies a leading position in methanol synthesis. It is generally accepted that the Cu/ZnO community is the active center, al 2 O 3 Mainly plays a role of a carrier, is used for stabilizing and dispersing the Cu/ZnO active center, and increases the thermal stability and the service life of the catalyst. Researches show that Cu and Zn are required to be uniformly dispersed in atomic scale for realizing high activity, al and Cu are unfavorable for the catalyst in atomic scale dispersion, the activity of the catalyst is greatly reduced, and Al is required for achieving sufficient stability 2 O 3 And dispersed homogeneously with Cu/ZnO nano-scale (Catalysis Today,1987, 2. Therefore, cu/ZnO/Al is industrially used 2 O 3 The catalyst is prepared by preparing a copper-zinc binary precursor and an aluminum carrier precursor into slurry by a precipitation method respectively, then mixing the two precursor slurries, and then carrying out washing, drying, roasting, forming and other steps to form the final catalyst.
Beating and mixing process of copper-zinc binary precursor slurry and aluminum carrier precursor slurry for Al 2 O 3 The mutual dispersion and bonding of the support and the Cu/ZnO active centers play a decisive role. The prior pulping mixing method is to pour the two slurries together and stir and mix the slurries, but the mixing method cannot fully and uniformly disperse the two precursor particles. Although the catalyst precursor particles are nanoparticles, the particle size of the single particles is within tens of nanometers, especially the particle size of the single particles of the aluminum carrier precursor is within tens of nanometers, the precursor is prepared by a precipitation method, and is in a sand-settling state and is not in a colloidal uniformly-dispersed state, in addition, the nanoparticles have extremely high surface energy and are easy to aggregate to form secondary particles, the particle size of the secondary particles is larger and can even be more than tens of micrometers (applied to chemical industry, 2021, doiTherefore, the nano-scale uniform dispersion of different precursor nano-particles cannot be well realized, and segregation aggregation of a carrier and a copper-zinc binary center is easily formed in the catalyst prepared by mixing, so that the stability of the catalyst is seriously influenced.
Disclosure of Invention
The invention aims to overcome the defects, and provides a pulping mixing process, which enables particles in slurry to be uniformly dispersed and combined in a nanoscale mode, is particularly suitable for mixing copper-zinc binary precursor slurry and aluminum carrier precursor slurry in the preparation process of a methanol synthesis catalyst, and prevents binary centers and carriers in a ternary precursor obtained by pulping and mixing from being unevenly distributed and segregated.
In order to realize the purpose, the invention is realized by the following technical scheme:
a pulping and mixing process comprising:
forming at least one of the slurries to be mixed into a colloidal slurry through a gelling reaction;
mixing the colloidal slurry with other slurry to be mixed to obtain blended slurry;
and (3) mixing the blending slurry by an ultrasonic dispersion-colloid mill for a plurality of times of circulating treatment until the particle size in the blending slurry is in single distribution and the change rate of the particle size along with the circulating treatment is less than 10%.
Further, the circulation treatment of ultrasonic dispersion-colloid mill mixing is to send the blended slurry in the ultrasonic pool into the colloid mill for mixing through a circulating pump, and send the slurry mixed by the colloid mill back into the ultrasonic pool for ultrasonic dispersion, and the process is a circulation.
Further, the slurry to be mixed at least comprises an aluminum-containing slurry. In the preparation process of the methanol synthesis catalyst, the slurry to be mixed comprises a carrier precursor slurry and a binary precursor slurry of the methanol synthesis catalyst. If only one of the slurry to be mixed is gelatinized, the gelatinized slurry can be uniformly mixed and dispersed with other slurry. Each slurry gels better, but not every slurry is suitable for gelling, and other slurries either gel poorly or the structure is destroyed.
Further, the gelling reaction is to use an acidic pH regulator to perform acidic pH regulation, so that the aluminum-containing slurry in the slurry to be mixed is in a colloid state or a colloid-like state.
Further, the acidic pH regulator is at least one of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, and the pH of the slurry after regulation is 4-6.
Further, after the acidic pH regulator is used for carrying out gelling reaction and pulping and mixing are completed, alkaline pH regulation is carried out through the alkaline pH regulator, so that after the pH of the blended slurry is neutral, circulation treatment is carried out again, the acid-base reaction is more thorough, and meanwhile, the slurry after alkaline pH regulation is uniformly dispersed, and the microenvironment of the slurry particles can be changed after alkaline pH regulation.
Further, the alkaline pH regulator is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
Further, the acidic pH adjustment is performed in a gelling tank, and the alkaline pH adjustment is performed in an ultrasonic tank.
Further, the gelling reaction and the ultrasonic dispersion are both performed under stirring conditions. The ultrasonic dispersion process may be performed at room temperature or under heating.
Further, the solid content of the slurry to be mixed is 10 g/L-300 g/L.
The precursor of the aluminum carrier can form jelly-like colloid state between pH 4-6, the nano particles are uniformly and stably dispersed, and the precipitate is not easy to precipitate after long-time placement, and is obviously different from the original neutral slurry which is easy to precipitate.
The ultrasonic wave is a mechanical wave with extremely short wavelength, when ultrasonic vibration is transmitted into liquid, strong cavitation effect can be excited in the liquid due to very high sound intensity, so that a large number of cavitation bubbles are generated in the liquid, the cavitation bubbles generate and explode at high frequency to generate microjet, and large-size secondary particles formed by aggregation in the liquid can be smashed and dispersed into primary particles.
Compared with the prior art, the invention has the beneficial effects that:
based on the problems that slurry turbid liquid is easy to settle and uneven in dispersion, and nanoparticles are easy to aggregate to form large-size secondary particles to cause segregation and aggregation of different slurry components, at least one slurry is made to be colloid or colloid-like to form an evenly-dispersed system, the secondary particles in precursor slurry are scattered into primary particles by using ultrasonic dispersion, on the basis of gelatinization and ultrasonic dispersion, a colloid mill is used for replacing common stirring, the slurry particles are efficiently mixed, the advantages of gelatinization, ultrasonic dispersion and colloid mill mixing are combined, and circulation treatment is carried out, so that nanoscale dispersion and combination of different slurry particles are facilitated, and segregation and aggregation of different combinations, particularly carrier components, are prevented.
The pulping mixing process is applied to mixing of the copper-zinc binary precursor slurry and the aluminum carrier precursor slurry in the preparation process of the methanol synthesis catalyst, and compared with the mode of directly stirring and mixing in the prior art, the prepared catalyst Cu/ZnO active center and Al 2 O 3 The carrier component is uniformly distributed in nanometer scale, and the carrier Al 2 O 3 The catalyst does not segregate and gather, can effectively disperse, isolate and stabilize the Cu/ZnO active center, prevents the active center components from migrating and agglomerating, and improves the stability of the catalyst.
Drawings
FIG. 1 is a schematic view of a pulping mixing process flow provided by an embodiment of the invention;
FIG. 2 is a photograph of HAADF and Al element distribution for example 5 (Cal-5);
FIG. 3 is a photograph of HAADF and a distribution diagram of Al element in comparative example 1 (Ref-1).
Detailed Description
Preferred embodiments of the present invention will be described in more detail below with reference to the accompanying drawings and specific examples.
The mass ratio of copper to zinc in the binary precursor of copper and zinc in terms of oxides used in the following examples is 3, and the final catalyst composition is controlled to be (CuO + ZnO) with a mass fraction of 90% in all the examples, and Al is controlled to be in the following ranges 2 O 3 The mass fraction is 10%.
Example 1
Diluting the carrier precursor slurry to a solid content of 23.5g/L, and adjusting the pH of the slurry to 6.0 by using dilute nitric acid in a gelling pool; diluting the binary precursor slurry to 125g/L of solid content, adding the two into an ultrasonic pool in equal volume, performing ultrasonic dispersion-colloid mill mixing circulation for three times at room temperature, adjusting the pH value of the slurry to be neutral by using sodium hydroxide, and performing ultrasonic dispersion-colloid mill mixing circulation treatment again until the particle size distribution does not change basically when the particle size detector detects the particle size distribution. And washing, drying, roasting and molding the mixed slurry subjected to the circulating dispersion and mixing treatment to obtain the catalyst Cat-1.
Example 2
Diluting the carrier precursor slurry to a solid content of 23.5g/L, and adjusting the pH of the slurry to 4.0 by using dilute nitric acid in a gelling pool; diluting the binary precursor slurry to 125g/L of solid content, adding the two into an ultrasonic pool in equal volume, carrying out ultrasonic dispersion-colloid mill mixing circulation for three times under the heating condition of 60-70 ℃, adjusting the pH value of the mixed slurry to be neutral by using sodium carbonate, and carrying out ultrasonic dispersion-colloid mill mixing circulation treatment again until the particle size distribution detected by a laser particle sizer does not change basically. And washing, drying, roasting and molding the mixed slurry subjected to the circulating dispersion and mixing treatment to obtain the catalyst Cat-2.
Example 3
Diluting the carrier precursor slurry to solid content of 10g/L, and adjusting the pH of the slurry to 5.0 by using dilute nitric acid in a gelling pool; diluting the binary precursor slurry to 50g/L of solid content, adding 106 parts of the binary precursor slurry and 100 parts of the carrier precursor slurry into an ultrasonic pool according to the volume, carrying out ultrasonic dispersion-colloid mill mixing circulation for three times at room temperature, adjusting the pH value of the mixed slurry to be neutral by using sodium bicarbonate, and carrying out ultrasonic dispersion-colloid mill mixing circulation treatment again until the particle size distribution does not change basically when the particle size distribution is detected by a laser particle sizer. And washing, drying, roasting and molding the mixed slurry subjected to the circulating dispersion and mixing treatment to obtain the catalyst Cat-3.
Example 4
Diluting the carrier precursor slurry to solid content of 100g/L, and adjusting the pH of the slurry to 5.0 by using dilute hydrochloric acid in a gelling pool; diluting the binary precursor slurry to the solid content of 300g/L, adding 177 parts of binary precursor slurry and 100 parts of carrier precursor slurry into an ultrasonic pool according to the volume, performing ultrasonic dispersion-colloid mill mixing circulation for four times under the heating condition of 60-70 ℃, adjusting the pH value of the mixed slurry to be neutral by using potassium carbonate, performing ultrasonic dispersion-colloid mill mixing circulation treatment again until the particle size distribution detected by a laser particle size analyzer does not change basically. And washing, drying, roasting and molding the mixed slurry subjected to the circulating dispersion and mixing treatment to obtain the catalyst Cat-4.
Example 5
Diluting the carrier precursor slurry to solid content of 9.4g/L, and adjusting the pH value of the slurry to 5.0 by using dilute hydrochloric acid in a gelling pool; diluting the binary precursor slurry to 50g/L of solid content, adding the two into an ultrasonic pool in equal volume, carrying out ultrasonic dispersion-colloid mill mixing circulation treatment for three times under the heating condition of 60-65 ℃, adjusting the pH value of the mixed slurry to be neutral by using potassium bicarbonate, and carrying out ultrasonic dispersion-colloid mill mixing circulation again until the particle size distribution does not change basically when the particle size is detected by a laser particle sizer. And washing, drying, roasting and forming the mixed slurry subjected to the circulating dispersion and mixing treatment to obtain the catalyst Cat-5. The HAADF photograph and Al element distribution are shown in FIG. 2.
Comparative example 1
The operation was the same as in example 5 except that the slurry of the support precursor was not subjected to pH adjustment to obtain a catalyst Ref-1. The HAADF photograph and Al element distribution are shown in FIG. 3.
Comparative example 2
The operation is the same as that of example 5, except that the carrier precursor slurry after pH adjustment and the binary precursor slurry are mixed by ordinary stirring, and the catalyst Ref-2 is obtained without ultrasonic dispersion-colloid mill mixing treatment.
Comparative example 3
The operation is the same as that of the embodiment 5, and the difference is that the binary precursor slurry and the carrier precursor slurry are directly and commonly stirred and uniformly mixed without pH adjustment and ultrasonic dispersion-colloid mill mixing treatment, so that the catalyst Ref-3 is obtained.
Example 6
And evaluating the performance of the catalyst obtained by the pulping and mixing process provided by the invention.
A micro fixed bed continuous flow reactor is adopted, the filling amount of the catalyst is 2mL, the granularity is 16 meshes to 40 meshes, and the reduction of the catalyst is carried out at low hydrogen (H) 2 :N 2 = 5) atmosphere, temperature programmed (20 ℃/h) to 230 ℃ for 10 hours. The reducing gas is switched into raw material gas for catalysisMethanol synthesis test. The test conditions are that the reaction pressure is 8.0MP, and the space velocity is 10000h -1 Temperature 230 ℃, composition of coal-based synthesis gas: h 2 :CO:CO 2 :N 2 And 4, 17 (v/v) and a small amount of sulfide of a reaction vessel, after the reaction is stable for 2 hours, emptying the liquid in the liquid collector and starting timing, cooling the collector by using circulating water, collecting the liquid (crude methanol) in the collector after 2.5 hours, and measuring the catalytic activity, namely the initial activity. Then the catalyst is heat treated for 5h at 400 ℃, and the activity is measured again under the conditions, namely the activity after heat resistance. Analyzing methanol, ethanol, propanol, hydrocarbon and the like in a liquid phase product by an Agilent-7890 gas chromatograph, carrying out chromatographic conditions, carrying out programmed temperature rise on a hydrogen Flame Ionization Detector (FID) and an HP-INNOWax type chromatographic column (the column is 60m in length, 0.32mm in inner diameter and 0.5 μm in wall thickness), using nitrogen as a carrier gas, carrying out injection at a sample inlet temperature of 250 ℃, carrying out constant pressure of 10psi, carrying out a flow splitting mode of 10, carrying out detection at a room temperature of 300 ℃, carrying out hydrogen flow of 30mL/min, carrying out air flow of 400mL/min and carrying out tail-blowing flow of 25mL/min, and quantifying by adopting an external standard method. The test results are shown in table 1.
TABLE 1 staged calcination of catalyst methanol Synthesis test results
From the test results, the catalyst prepared by the pulping mixing process of the invention has better heat-resistant stability than the catalyst prepared by conventional stirring mixing, and shows the superiority of the invention.
It should be noted that the above mentioned embodiments are only preferred embodiments of the present invention, and it is obvious to those skilled in the art that several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention. Although the present invention is directed to Cu/ZnO/Al 2 O 3 The binary precursor and the carrier precursor of the methanol synthesis catalyst are pulped and mixed, but the same pulping and mixing process can be adopted for other catalysts which relate to the pulping and mixing preparation steps of two or more different slurries, and the transplantation, popularization and application of the catalysts also need to be carried out in the inventionWithin the scope of protection of (1).
Claims (10)
1. A pulping and mixing process is characterized by comprising the following steps:
forming at least one of the slurries to be mixed into a colloidal slurry through a gelling reaction;
mixing the colloidal slurry with other slurry to be mixed to obtain blended slurry;
and (3) mixing the blended slurry through an ultrasonic dispersion-colloid mill for a plurality of times of circulating treatment until the particle size in the blended slurry is in single distribution and the change rate of the particle size along with the circulating treatment is less than 10%.
2. The pulping mixing process according to claim 1, wherein the circulation treatment of the ultrasonic dispersion-colloid mill mixing is to send the blended slurry in the ultrasonic pool into the colloid mill for mixing through a circulation pump, and send the slurry mixed by the colloid mill back into the ultrasonic pool for ultrasonic dispersion, and the process is a circulation.
3. The pulping mixing process of claim 1 or 2, wherein the slurry to be mixed comprises at least one aluminum-containing slurry.
4. The pulping mixing process according to claim 3, wherein the gelling reaction is acidic pH adjustment by using an acidic pH adjusting agent, so that the aluminum-containing slurry in the slurry to be mixed is formed into a colloid shape or a colloid-like shape.
5. The pulping mixing process according to claim 4, wherein the acidic pH regulator is at least one of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, and the pH of the slurry after regulation is 4-6.
6. The pulping mixing process according to claim 4, wherein the gelling reaction is carried out by using an acidic pH regulator, and after the completion of the pulping mixing, the alkaline pH regulation is carried out by using an alkaline pH regulator to make the pH of the blended slurry neutral, and then the recycling treatment is carried out again.
7. The pulping mixing process of claim 6, wherein the alkaline pH adjuster is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.
8. The beater mixing process according to claim 6, wherein the acidic pH adjustment is performed in a gelling tank and the basic pH adjustment is performed in an ultrasonic tank.
9. The beater mixing process according to claim 1, wherein the gelling reaction and the ultrasonic dispersion are both carried out under stirring conditions.
10. The pulping mixing process according to claim 1, wherein the solid content of the slurry to be mixed is 10 g/L-300 g/L.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310070519.6A CN115945226A (en) | 2023-02-07 | 2023-02-07 | Pulping and mixing process |
Applications Claiming Priority (1)
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| CN103480377A (en) * | 2012-06-15 | 2014-01-01 | 中国石油化工股份有限公司 | Preparation method of copper based catalyst for methanol synthesis |
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| CN110935455A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of copper-zinc catalyst |
| CN112011190A (en) * | 2019-05-31 | 2020-12-01 | 中国石油天然气股份有限公司 | Polymer gel, particle size distribution monodisperse polymer microsphere, preparation and application thereof |
| CN114732828A (en) * | 2022-04-27 | 2022-07-12 | 广西南宁百会药业集团有限公司 | Hydrotalcite suspension and preparation method thereof |
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| CN106179437A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of the ultra-fine parent of Cu base methanol synthetic catalyst |
| EP3305404A1 (en) * | 2016-10-10 | 2018-04-11 | National Petrochemical Company | Copper/zinc/aluminium catalyst for the methanol synthesis prepared from a binary zinc-aluminium precursor solution |
| WO2018069759A1 (en) * | 2016-10-10 | 2018-04-19 | National Petrochemical Company | Copper/zinc/aluminium catalyst for the methanol synthesis prepared from a binary zinc-aluminium precursor solution |
| CN110935455A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of copper-zinc catalyst |
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