CN112744849A - Method for producing aluminum sol and aluminum sol - Google Patents
Method for producing aluminum sol and aluminum sol Download PDFInfo
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- CN112744849A CN112744849A CN201911054709.9A CN201911054709A CN112744849A CN 112744849 A CN112744849 A CN 112744849A CN 201911054709 A CN201911054709 A CN 201911054709A CN 112744849 A CN112744849 A CN 112744849A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0043—Preparation of sols containing elemental metal
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
The invention relates to the field of preparation of aluminum sol, and discloses a preparation method of aluminum sol and the aluminum sol, wherein the method comprises the following steps: (1) carrying out first contact on a first aluminum source and a first alkali source to obtain a first reaction solution, wherein the pH of the first reaction solution is 3-5; (2) carrying out second contact on the first reaction liquid, a second aluminum source and a second alkali source to obtain a second reaction liquid, wherein the pH value of the second reaction liquid is 3-4.5; (3) and carrying out second aging on the second reaction liquid, wherein the second aging is carried out at the temperature of not more than 100 ℃. The method provided by the invention has the advantages of low cost of raw materials, mild conditions in the synthesis process, no hydrogen generation, low equipment corrosivity and Al-based composition of the obtained alumina sol product13Mainly comprises the following steps.
Description
Technical Field
The invention relates to the field of preparation of aluminum sol, in particular to a preparation method of aluminum sol and the aluminum sol prepared by the preparation method.
Background
The alumina sol is a colloidal solution in which positively charged fine particles of hydrated alumina are uniformly dispersed in water. Currently, aluminum sols are widely used in industry as catalyst binders and water treatment flocculants. The nomenclature of the aluminium sols varies according to the field of application, for example: when used in a catalyst binder, is commonly referred to as an alumina sol; when used in a flocculant, the flocculant is referred to as polyaluminum chloride or aluminum chlorohydrate, but the structural formula of the flocculant can be expressed as follows: [ Al ]2(OH)nCl6-n·xH2O]m(n＝1-5，m>0)。
The properties of the aluminum sol can be generally expressed by the aluminum content, the aluminum-chlorine ratio (i.e., the ratio of aluminum element to chlorine element, either by weight or by mole), or the degree of base, which is the molar ratio of hydroxide to aluminum in the polyaluminum chloride.
The preparation method of the aluminum sol is various, and the common preparation method mainly comprises the following steps: the metal aluminum method, the organic alkoxide hydrolysis method, the electrolysis method, the inorganic salt raw material method, the powder dispersion method and the like, wherein the metal aluminum method for preparing aluminum sol by adopting metal aluminum and hydrochloric acid is still the main production method.
US4028216A describes in detail the preparation of metal aluminium sol at the earliest, which is simple and easy to operate, but since the aluminium sol is prepared from aluminium hydroxide, the production cost is too high and a large amount of electric energy is consumed, and the hydrogen generated during the preparation also brings about a safety hazard and the hydrochloric acid used corrodes the equipment.
The organic alkoxide hydrolysis method can prepare sol with high purity, large specific surface and uniform particle size distribution. The method is suitable for preparing the alumina powder with high purity requirement. However, the greatest difficulty in the preparation process of the method is that the raw materials are sensitive to water, the hydrolysis reaction is very rapid, precipitates are easy to form, and the raw materials are expensive, flammable, toxic, difficult to store and bring difficulty to industrialization.
CN1177653A reports that the aluminum sol is prepared by adopting an electrolytic method, the polyaluminium chloride is synthesized by an electrochemical method with low voltage and large current, and a common anionic membrane with low price is adopted, so that the preparation cost of the product is reduced, and the method is relatively environment-friendly. However, the electrolytic water consumption is excessive, the initial cost is high (electrodes are needed in the repeating unit), chlorine gas may be generated, and potential safety hazards exist.
The inorganic salt raw material method has the advantages of low price of raw materials, simple method and lower production cost of the aluminum sol, but the purity of the sol is lower.
The alumina sol prepared by the powder dispersion method omits a hydrolysis step, the process is simple, and the raw materials are industrial products, so that the price is low, the storage is convenient, and the industrialization is easy to realize. However, the raw materials often contain impurities, and the purity of the prepared aluminum sol is relatively low.
Nowadays, the environmental protection requirements in the industrial development and production process are becoming more and more strict, and the atom economy of the reaction process is more and more important, so that the search for a new low-cost and efficient preparation method of aluminum sol becomes more and more important.
Disclosure of Invention
The invention aims to provide an alumina sol preparation method with high raw material utilization rate and the alumina sol prepared by the preparation method, the method has the advantages of low cost of the used raw materials, mild conditions in the synthesis process, no hydrogen generation, low equipment corrosivity and Al-based product composition13Mainly comprises the following steps.
The first aspect of the present invention provides a method for preparing an aluminum sol, comprising:
(1) carrying out first contact on a first aluminum source and a first alkali source to obtain a first reaction solution, wherein the pH of the first reaction solution is 3-5;
(2) carrying out second contact on the first reaction liquid, a second aluminum source and a second alkali source to obtain a second reaction liquid, wherein the pH value of the second reaction liquid is 3-4.5;
(3) and carrying out second aging on the second reaction liquid, wherein the second aging is carried out at the temperature of not more than 100 ℃.
The second aspect of the invention provides an aluminum sol obtained by the preparation method, wherein Al is used in the aluminum sol2O3The aluminum content is 5 to 30% by weight.
Preferably, in the aluminum sol, the Al element is mainly Al13The form exists.
The preparation method of the aluminum sol and the aluminum sol prepared by the preparation method have the following advantages:
(1) the adopted raw materials are low in price and high in utilization rate, so that the preparation cost is low;
(2) the whole preparation process has mild conditions, low reaction temperature and short reaction period;
(3) the prepared alumina sol has good quality, high purity and low impurity content;
(4) the Al element in the alumina sol prepared by the preparation method is mainly Al13Form (a) of Al13The existence of the aluminum sol enables the aluminum sol to have better cohesiveness, and when the aluminum sol is used in a catalyst, the pore volume of the catalyst can be better reserved, the phenomenon of pore blocking existing when the traditional aluminum sol is used in the catalyst is overcome, and the yield and the conversion rate of liquefied gas and gasoline of the catalyst are more favorably improved.
Drawings
FIG. 1 shows an aluminum sol S1 obtained in example 1 of the present invention27Al NMR spectrum.
FIG. 2 shows the preparation of an aluminum sol D1 prepared in comparative example 1 of the present invention27Al NMR spectrum.
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 present invention provides a method for preparing an aluminum sol, comprising:
(1) carrying out first contact on a first aluminum source and a first alkali source to obtain a first reaction solution, wherein the pH of the first reaction solution is 3-5;
(2) carrying out second contact on the first reaction liquid, a second aluminum source and a second alkali source to obtain a second reaction liquid, wherein the pH value of the second reaction liquid is 3-4.5;
(3) and carrying out second aging on the second reaction liquid, wherein the second aging is carried out at the temperature of not more than 100 ℃.
According to the present invention, the first aluminum source and the second aluminum source may be the same or different, and preferably, each of the first aluminum source and the second aluminum source is independently at least one selected from the group consisting of an aluminum salt, polyaluminum chloride, and aluminum isopropoxide. Further preferably, the aluminum salt is selected from at least one of aluminum chloride, aluminum nitrate and aluminum sulfate. The polyaluminum chloride can be commercial polyaluminum chloride.
According to a preferred embodiment of the invention, the first aluminium source is aluminium chloride. Specifically, the first aluminum source may be used in the form of a solution. Specifically, the concentration of the first aluminum source may be 1 to 32 wt%.
According to a preferred embodiment of the present invention, the second aluminum source is selected from at least one of aluminum chloride, polyaluminum chloride and aluminum isopropoxide, preferably polyaluminum chloride.
In the research process, the inventor of the present invention finds that when the first aluminum source is aluminum chloride and the second aluminum source is polyaluminum chloride, it is more beneficial to reduce the subsequent concentration pressure.
The terms "first" and "second" are not used in any limiting sense, but are used to distinguish between operations performed at different stages or between materials added at different stages.
In the present invention, the first alkali source and the second alkali source may be the same or different, and the alkali may be an alkali substance sufficient to convert the aluminum source into the aluminum sol. Preferably, the first and second alkali sources are each independently selected from the group consisting of alkali metal hydroxide, NH3·H2O and an organic base. Specific examples of the alkali metal hydroxide may include, but are not limited to, NaOH and/or KOH. Specific examples of the organic base may include, but are not limited to, at least one of n-butylamine, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
The first and second sources of base are typically provided in the form of aqueous solutions. The concentration of the first and second alkalinity sources in the aqueous solution may be selected according to the type of alkalinity source, for example: for aqueous ammonia, the concentration may be 1 to 25% by weight, preferably 2 to 20% by weight; for alkali metal hydroxides, the concentration may be from 5 to 20% by weight, preferably from 12 to 18% by weight; for the organic base, the concentration thereof may be 3 to 20% by weight, preferably 5 to 15% by weight.
The amounts of the first alkali source and the second alkali source can be selected according to the amounts of the first aluminum source and the second aluminum source. Preferably, the mass ratio of the total amount of the first alkali source and the second alkali source to the total amount of the first aluminum source and the second aluminum source is (0.2-1.5): 1, preferably (0.3-1): 1, more preferably (0.39-0.6): 1, the first and second alkali sources are substituted with OH-And/or N, wherein the first aluminum source and the second aluminum source are calculated by aluminum element. When the alkali source contains OH-Or N, the amount of the alkali source is OH-Or N is counted; when the alkali source contains OH-When N is used, the amount of the alkali source is OH-And (6) counting. For example, tetrapropylammonium hydroxide is used in an amount of OH-And (6) counting.
According to a preferred embodiment of the present invention, the mass ratio of the first aluminum source to the second aluminum source is (0.1-2): 1, preferably (0.3-1.5): 1, more preferably (0.5-1): 1, more preferably (0.59-0.73): 1.
according to the preparation method provided by the present invention, in the step (1), the first aluminum source and the first alkali source may be subjected to the first contact under conventional conditions, for example, normal temperature (25 ℃) and normal pressure. Typically, the duration of the first contact is sufficient to convert the first source of aluminum to a salt-containing aluminum sol and is based on a pH of 3 to 5, typically the duration of the first contact may be 1 to 24 hours, preferably 2 to 18 hours. From the viewpoint of further improving the uniformity of the contact reaction, the first contact is preferably carried out under conditions accompanied by stirring.
According to a preferred embodiment of the present invention, the pH of the first reaction solution is 3 to 5, more preferably 3 to 4.5, and still more preferably 3.3 to 4.5.
According to the present invention, preferably, the method further comprises: and (2) carrying out first aging on the first reaction solution in the step (1), and then carrying out the step (2).
According to a preferred embodiment of the present invention, a method for preparing an aluminum sol comprises:
(1) carrying out first contact on a first aluminum source and a first alkali source to obtain a first reaction solution, wherein the pH of the first reaction solution is 3-4.5; subjecting the first reaction solution to a first aging, the first aging being performed at a temperature of not more than 100 ℃;
(2) carrying out second contact on the reaction liquid after the first aging in the step (1), a second aluminum source and a second alkali source to obtain a second reaction liquid, wherein the pH value of the second reaction liquid is 3-4.5;
(3) and carrying out second aging on the second reaction liquid, wherein the second aging is carried out at the temperature of not more than 100 ℃.
According to the invention, preferably, the first ageing is carried out at a temperature of between 30 and 95 ℃, preferably between 30 and 70 ℃, more preferably between 35 and 55 ℃.
According to the present invention, it is further preferred that the time of the first aging is 10 to 120min, preferably 20 to 60 min.
In the step (2) of the present invention, the first reaction solution obtained in the step (1) is preferably contacted with the second aluminum source and the second alkali source in the second contact with stirring, from the viewpoint of further improving the uniformity of the contact reaction.
According to the present invention, the pH of the second reaction solution is 3 to 4.5, more preferably 3.5 to 4.5, and still more preferably 3.7 to 4.5.
According to the invention, the temperature of the second ageing is preferably at least 10 ℃ higher, preferably between 10 and 35 ℃ higher, and more preferably between 15 and 30 ℃ higher than the temperature of the first ageing.
According to a preferred embodiment of the invention, the second aging is carried out at a temperature of 40 to 95 ℃, preferably 40 to 80 ℃, more preferably 60 to 80 ℃, even more preferably 70 to 80 ℃.
According to a preferred embodiment of the invention, the second aging is carried out for a period of 3 to 10 hours, preferably 4 to 8 hours.
According to the invention, preferably, the first aging and the second aging are each independently carried out under stirring conditions.
The stirring in the above different steps is not particularly limited in the present invention, and may be conventional mechanical stirring or magnetic stirring.
According to the present invention, the preparation method is not limited to only two contacts with the alkali source and aging. Preferably, the preparation method provided by the invention can further comprise repeating the step (2) and the step (3). Namely, the heated solution obtained in the step (3) is brought into contact with an aluminum source and an alkali source to obtain a reaction solution having a pH of 3 to 4.5, and the reaction solution is aged again.
According to the preparation method of the aluminum sol, the obtained aluminum sol can be directly output as an aluminum sol product, can be output as the aluminum sol product after partial solvent in the aluminum sol is removed, and can also be output after desalination.
According to the method for preparing the aluminum sol of the present invention, a part of the solvent in the aluminum sol can be removed by a conventional method, and preferably, the method further comprises: the concentration of the aluminum sol obtained in step (3) can be carried out, for example, by removing a part of the solvent from the aluminum sol by evaporation, which can be carried out at a temperature of 50 to 150 ℃, preferably at a temperature of 70 to 120 ℃, and more preferably at a temperature of 80 to 95 ℃. The amount of the solvent to be removed can be selected according to the specific application of the aluminum sol. Preferably, the concentration is such that Al is present in the aluminium sol2O3The aluminum content is 15 to 30% by weight, preferably 15 to 25% by weight, and the aluminum sol is particularly suitable as a binder for catalysts.
According to the second aspect of the invention, the invention also provides the aluminum sol obtained by the preparation method, and the aluminumIn the sol, with Al2O3The aluminum content is 5 to 30% by weight.
Preferably, in the aluminum sol, the Al element is mainly Al13The form exists. The Al element is mainly Al13The formal presence means that 50% or more of the Al element is present as Al13The form exists. The Al element can exist in a form of27And determining an Al NMR spectrum. In that27Al is Al at delta 60-61 in an Al NMR spectrum13The characteristic peak of the tetra-coordinated aluminum is that the delta is Al at the position of 10-1213And/or Al30Delta is 0, the characteristic peak of the monomer aluminum. The Al can be determined according to the peak area of the characteristic peak13Amount of Al element formally present.
According to a preferred embodiment of the present invention, the aluminum sol has an aluminum-chlorine mass ratio of 1 to 1.4, more preferably 1 to 1.2.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples, the content of aluminum in the prepared aluminum sol product was measured by the method specified in RIPP34-90, the pH of the aluminum sol was measured by a pH meter (available from Mettler-Torlo), and the form of Al element in the aluminum sol was measured by a nuclear magnetic resonance spectrometer.
Example 1
(1) 515g of ammonia water having a concentration of 15% by weight was slowly added to 900g of an aluminum chloride solution having a concentration of 20% by weight with stirring at ambient temperature (25 ℃ C., the same applies hereinafter), and the mixture was stirred for 0.5 hour to obtain a first reaction solution having a pH of 3.4;
(2) raising the temperature of the first reaction liquid to 50 ℃, and stirring and reacting for 0.5 hour at the temperature;
(3) introducing 200g of polyaluminum chloride (containing 51.06g of Al element) into the heated solution obtained in the step (2) with stirring, and adding 190g of aqueous ammonia having a concentration of 20% by weight to obtain a second reaction solution having a pH of 3.9;
(4) the temperature of the second reaction solution was raised to 80 ℃ and stirred at this temperature for 3 hours, then cooled to ambient temperature to give a concentration of 5.4 wt.% (in terms of Al)2O3Calculated), the aluminum-chlorine mass ratio of the aluminum sol S1 to the aluminum sol S1 was 1.1.
Of aluminium sol S127The NMR spectrum of Al is shown in FIG. 1, and it can be seen from FIG. 1 that Al exists at a delta of 60 to 6113The characteristic peak of monomeric aluminum is present at a position where δ is 0, and it can be seen that the Al element is mainly Al13The form exists.
Comparative example 1
With stirring, 50g of aluminum ingot was put into 400g of concentrated hydrochloric acid (37 wt%), heated to 85 ℃ and kept at the temperature for 7 hours to obtain a concentration of 20.9 wt% (as Al)2O3Calculated), the aluminum-chlorine mass ratio of the aluminum sol D1 to the aluminum sol D1 was 1. Of alumina sol D127The NMR spectrum of Al is shown in FIG. 2, and it can be seen from FIG. 2 that Al exists at a delta of 60 to 6113But the characteristic peak of the four-coordinate aluminum is weaker, the characteristic peak of the monomer aluminum exists at delta of 0, and Al exists at delta of 10-1213And/or Al30And a characteristic peak of dimeric aluminium is present at δ from 2 to 3.
Example 2
(1) 660g of a 15 wt% aqueous sodium hydroxide solution was slowly added to 920g of a 20 wt% aqueous aluminum chloride solution at ambient temperature (25 ℃ C., the same applies hereinafter) with stirring, and the mixture was stirred for 1 hour to obtain a first reaction solution having a pH of 3.3;
(2) raising the temperature of the first reaction liquid to 55 ℃, and stirring and reacting for 1 hour at the temperature;
(3) introducing 200g of polyaluminum chloride (containing 51.06g of Al element) into the heated solution obtained in the step (2) with stirring, and adding 100g of a 20% by weight sodium hydroxide solution to obtain a second reaction solution having a pH of 3.8;
(4) the temperature of the second reaction solution was raised to 80 ℃ and stirred at this temperature for 4.5 hours, then cooled to ambient temperature to give a concentration of 4.9 wt.% (expressed as Al)2O3Calculated), the aluminum-chlorine mass ratio of the aluminum sol S2 to the aluminum sol S2 was 1.05.
Of aluminium sol S227Al NMR spectrum similar to FIG. 1With Al present at delta of 60-6113The characteristic peak of monomeric aluminum is present at a position where δ is 0, and it can be seen that the Al element is mainly Al13The form exists.
Example 3
(1) 515g of ammonia water having a concentration of 15% by weight was slowly added to 900g of an aluminum chloride solution having a concentration of 20% by weight with stirring at ambient temperature (25 ℃ C., the same applies hereinafter), and the mixture was stirred for 0.5 hour to obtain a first reaction solution having a pH of 3.4;
(2) the temperature of the first reaction liquid was raised to 50 ℃ and the reaction was stirred at that temperature for 0.5 hour.
(3) Introducing 200g of polyaluminum chloride (having an Al element content of 51.06g) into the heated solution obtained in step (2) with stirring, and adding 352g of a 15% by weight n-butylamine solution to obtain a second reaction solution having a pH of 4.1;
(4) the temperature of the second reaction solution was raised to 80 ℃ and stirred at this temperature for 4 hours, then cooled to ambient temperature to give a concentration of 4.7% by weight (as Al)2O3Meter) of aluminum sol.
(5) Concentrating: stirring the alumina sol obtained in the step (4) at the temperature of 85 ℃ for 2 hours to remove part of water to obtain the alumina sol with the concentration of 19.9 weight percent (based on Al)2O3Meter) of aluminum sol S3. The aluminum-chlorine mass ratio of the aluminum sol S3 was found to be 1.2.
Of aluminium sol S327The Al NMR spectrum is similar to that of FIG. 1, and it can be seen from FIG. 1 that Al is present at a delta of 60 to 6113The characteristic peak of monomeric aluminum is present at a position where δ is 0, and it can be seen that the Al element is mainly Al13The form exists.
Example 4
(1) While stirring, 480g of a 15 wt% aqueous potassium hydroxide solution was slowly added to 750g of a 20 wt% aluminum chloride solution at ambient temperature (25 ℃ C., the same applies hereinafter), and the mixture was stirred for 0.5 hour to obtain a first reaction solution having a pH of 3.3;
(2) raising the temperature of the first reaction liquid to 50 ℃, and stirring and reacting for 0.5 hour at the temperature;
(3) introducing 200g of polyaluminum chloride (containing 51.06g of Al element) into the heated solution obtained in the step (2) with stirring, and adding 220g of a 15% by weight aqueous solution of potassium hydroxide to obtain a second reaction solution having a pH of 4.5;
(4) the temperature of the second reaction solution was raised to 70 ℃ and stirred at this temperature for 4.5 hours, then cooled to ambient temperature to give a concentration of 4.8 wt.% (expressed as Al)2O3Calculated), the aluminum-chlorine mass ratio of the aluminum sol S4 to the aluminum sol S4 was 1.
Of aluminium sol S427The Al NMR spectrum is similar to that of FIG. 1, with Al present at delta 60-6113The characteristic peak of monomeric aluminum is present at a position where δ is 0, and it can be seen that the Al element is mainly Al13The form exists.
Example 5
The method of example 1 was followed except that the first reaction solution in step (2) and the second reaction solution in step (4) were both heated to 50 ℃ and the stirring reaction time in step (4) was extended to 8 hours. A concentration of 5.8% by weight (in terms of Al) is obtained2O3Calculated by weight), the aluminum sol S5 had an aluminum-chlorine mass ratio of 1.05 for the aluminum sol S5.
Of aluminium sol S527The Al NMR spectrum is similar to that of FIG. 1, with Al present at delta 60-6113The characteristic peak of monomeric aluminum is present at a position where δ is 0, and it can be seen that the Al element is mainly Al13The form exists.
Example 6
The procedure of example 1 was followed, except that the first reaction solution in the step (2) and the second reaction solution in the step (4) were both heated to 80 ℃. A concentration of 5.5% by weight (in terms of Al) is obtained2O3Calculated by weight), the aluminum sol S6 had an aluminum-chlorine mass ratio of 1.05 for the aluminum sol S6.
Of aluminium sol S627The Al NMR spectrum is similar to that of FIG. 1, with Al present at delta 60-6113The characteristic peak of monomeric aluminum is present at a position where δ is 0, and it can be seen that the Al element is mainly Al13The form exists.
Example 7
The process of example 1 is followed, except that step (1) introduces polyaluminium chloride and step (3) introduces aluminium chloride, in particular:
(1) 515g of ammonia water having a concentration of 15% by weight was slowly added to 900g of a 20% by weight polyaluminum chloride solution (containing 45.96g of Al element) at ambient temperature (25 ℃ C., the same applies hereinafter) with stirring, and the mixture was stirred for 0.5 hour to obtain a first reaction solution having a pH of 3.5;
(2) raising the temperature of the first reaction liquid to 50 ℃, and stirring and reacting for 0.5 hour at the temperature;
(3) introducing 200g of aluminum chloride into the heated solution obtained in the step (2) with stirring, and adding 190g of aqueous ammonia having a concentration of 20% by weight to obtain a second reaction solution having a pH of 3.7;
(4) the temperature of the second reaction solution was raised to 80 ℃ and stirred at this temperature for 3 hours, then cooled to ambient temperature to give a concentration of 5.04 wt.% (expressed as Al)2O3Calculated), the aluminum-chlorine mass ratio of the aluminum sol S7 to the aluminum sol S7 was 1.
Of aluminium sol S727The Al NMR spectrum is similar to that of FIG. 1, with Al present at delta 60-6113The characteristic peak of monomeric aluminum is present at a position where δ is 0, and it can be seen that the Al element is mainly Al13The form exists.
As can be seen from the above examples and comparative examples, the method of the present invention can produce high quality alumina sol products, and the adopted raw materials have low price and high utilization rate of the raw materials, so the production cost is low; the whole production process has mild conditions, low reaction temperature and short reaction period. As no additional impurities are required to be introduced in the preparation process, the prepared aluminum sol has low impurity content. In addition, Al element in the aluminum sol prepared by the production method mainly exists in a four-coordinate aluminum form.
Test example 1
This test example is used to illustrate the performance of the aluminum sol provided by the present invention as a binder for a catalyst. The preparation method of the catalyst comprises the following steps:
pulping kaolin with water, and adding acidifiedPseudo-boehmite (pseudo-boehmite is mixed with water, then hydrochloric acid is added into the pseudo-boehmite under the stirring condition for acidification until the pseudo-boehmite is in a peptized state), and the pseudo-boehmite is stirred to obtain slurry A with the solid content of 40 weight percent; pulping a ZSM-5 molecular sieve with water to obtain molecular sieve slurry (the solid content is 30 weight percent); slurry A and a molecular sieve slurry were added to the alumina sols obtained in the above examples and comparative examples, respectively, and stirred for 30min to obtain a catalyst slurry (having a solid content of 30 wt%), wherein the catalyst slurry had a ZSM-5 molecular sieve content of 30 wt%, a kaolin content of 42 wt%, and an alumina sol content (in terms of Al) based on the dry weight of the catalyst slurry2O3Calculated) was 12 wt%; content of pseudo-boehmite in terms of Al2O3Calculated) was 16 wt%. And (3) carrying out spray drying on the catalyst slurry, and roasting the obtained catalyst microspheres for 1 hour at 550 ℃ to obtain the catalytic cracking catalyst.
Catalyst characterization:
the pore structure of the catalyst was analyzed by BET and the results are shown in table 1 below. As can be seen from Table 1, the catalyst prepared by using the aluminum sol provided by the present invention has better retention of pores than the catalyst prepared by using the aluminum sol of the prior art.
TABLE 1
Evaluation of catalyst:
the catalyst is subjected to hydrothermal aging treatment for 17 hours at 800 ℃ by 100 percent water vapor, and then heavy oil micro-reverse evaluation is carried out. The reaction raw materials are Wu-mix triple oil, and the raw materials are shown in Table 2. The catalyst loading is 5g, the reaction temperature is 460 ℃, and the weight space velocity is 16 hours-1The agent-oil ratio (by weight) is 4. The catalytic performance data are shown in table 3 below.
Wherein, the conversion rate is gasoline yield, liquefied gas yield, dry gas yield and coke yield
TABLE 2
TABLE 3
As can be seen from table 3, the use of the alumina sol provided by the present invention as a binder in a catalyst enables the catalyst to have further improved yields of liquefied gas and gasoline and conversion rate compared with conventional catalysts.
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 (10)
1. A method of preparing an aluminum sol, the method comprising:
(1) carrying out first contact on a first aluminum source and a first alkali source to obtain a first reaction solution, wherein the pH of the first reaction solution is 3-5;
(2) carrying out second contact on the first reaction liquid, a second aluminum source and a second alkali source to obtain a second reaction liquid, wherein the pH value of the second reaction liquid is 3-4.5;
(3) and carrying out second aging on the second reaction liquid, wherein the second aging is carried out at the temperature of not more than 100 ℃.
2. The method of claim 1 wherein the first and second aluminum sources are each independently selected from at least one of an aluminum salt, a polyaluminum chloride, and an aluminum isopropoxide; preferably, the aluminum salt is selected from at least one of aluminum chloride, aluminum nitrate, and aluminum sulfate;
further preferably, the first aluminum source is aluminum chloride, preferably the first aluminum source is used in the form of a solution;
further preferably, the second aluminum source is selected from at least one of aluminum chloride, polyaluminum chloride and aluminum isopropoxide, preferably polyaluminum chloride.
3. The method of claim 1, wherein the first and second base sources are each independently selected from the group consisting of alkali metal hydroxide, NH3·H2At least one of O and an organic base;
preferably, the alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide;
preferably, the organic base is selected from at least one of n-butylamine, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
4. The method of any of claims 1-3, wherein the mass ratio of the total amount of the first and second soda sources to the total amount of the first and second aluminum sources is (0.2-1.5): 1, preferably (0.3-1): 1, the first and second alkali sources are substituted with OH-And/or N, wherein the first aluminum source and the second aluminum source are calculated by aluminum element;
preferably, the mass ratio of the first aluminum source to the second aluminum source is (0.1-2): 1, more preferably (0.3 to 1.5): 1, more preferably (0.5-1): 1.
5. the method according to any one of claims 1 to 4, wherein the pH of the first reaction solution is 3 to 4.5;
preferably, the method further comprises: carrying out first aging on the first reaction solution in the step (1), and then carrying out the step (2);
further preferably, the first aging is carried out at a temperature of 30 to 95 ℃, preferably 30 to 70 ℃, more preferably 35 to 55 ℃;
further preferably, the first aging time is 10-120min, preferably 20-60 min.
6. The method according to claim 5, wherein the temperature of the second ageing is at least 10 ℃, preferably 10-35 ℃, further preferably 15-30 ℃ higher than the temperature of the first ageing.
7. The method according to any one of claims 1-6, wherein the second aging is performed at a temperature of 40-95 ℃, preferably 40-80 ℃, more preferably 60-80 ℃;
preferably, the second aging time is 3 to 10 hours, preferably 4 to 8 hours.
8. The method according to any one of claims 1 to 6, wherein the pH of the second reaction solution is 3.5 to 4.5.
9. The method of any one of claims 1-8, wherein the method further comprises: concentrating the alumina sol obtained in the step (3); preferably, the concentration is such that Al is present in the aluminium sol2O3The aluminum content is 15-30 wt.%.
10. The aluminum sol obtained by the production method according to any one of claims 1 to 9, wherein the aluminum sol contains Al2O3The calculated aluminum content is 5-30 wt%;
preferably, in the aluminum sol, the Al element is mainly Al13The form exists;
further preferably, the aluminum-chlorine mass ratio of the aluminum sol is 1 to 1.4.
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