CN117326935A - Aluminum citrate and preparation method thereof - Google Patents
Aluminum citrate and preparation method thereof Download PDFInfo
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- CN117326935A CN117326935A CN202311283993.3A CN202311283993A CN117326935A CN 117326935 A CN117326935 A CN 117326935A CN 202311283993 A CN202311283993 A CN 202311283993A CN 117326935 A CN117326935 A CN 117326935A
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- ZUGAOYSWHHGDJY-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-aluminabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Al+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZUGAOYSWHHGDJY-UHFFFAOYSA-K 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 51
- 238000002156 mixing Methods 0.000 claims abstract description 43
- 239000002243 precursor Substances 0.000 claims abstract description 43
- 230000002378 acidificating effect Effects 0.000 claims abstract description 42
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012670 alkaline solution Substances 0.000 claims abstract description 41
- 239000012266 salt solution Substances 0.000 claims abstract description 41
- 238000003756 stirring Methods 0.000 claims abstract description 41
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- -1 aluminum ions Chemical class 0.000 claims abstract description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 44
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000000536 complexating effect Effects 0.000 abstract description 2
- 229940063656 aluminum chloride Drugs 0.000 description 20
- 230000000694 effects Effects 0.000 description 14
- 229960004106 citric acid Drugs 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 4
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229960002303 citric acid monohydrate Drugs 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/265—Citric acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The application relates to aluminum citrate and a preparation method thereof, wherein the method comprises the following steps: mixing an acidic aluminum salt solution and an alkaline solution through first stirring, controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution, and then drying and crushing to obtain alumina hydrate precursor powder; and carrying out second stirring and mixing on the alumina hydrate precursor powder and the citric acid solution to obtain aluminum citrate. The method solves the technical problem of higher energy consumption of the existing preparation process of the aluminum citrate, and can effectively improve A in the aluminum citrate solution l3+ Content, improved complexing effect, product Al 3+ The content is more than or equal to 8 weight percent.
Description
Technical Field
The application relates to the technical field of aluminum-based powder materials, in particular to aluminum citrate and a preparation method thereof.
Background
The aluminum citrate can be used as a cross-linking agent, and is mixed with Polyacrylamide (PAM) to gradually form a reticular gel, so that the reticular gel is used for plugging water and controlling profile of an oil field and plugging a high permeable layer of the oil field.
Aluminum citrate as a crosslinking agent, al 3+ The higher the content of the active ingredient, the better the complexation effect. The existing preparation of aluminum citrate needs to be carried out at high temperature for a long time, the energy consumption is high, and the aluminum citrate contains Al 3+ The content of (2) is small, resulting in poor complexation effect.
Disclosure of Invention
The application provides aluminum citrate and a preparation method thereof, which are used for solving the technical problem of higher energy consumption of the existing aluminum citrate preparation process.
In a first aspect, the present application provides a method for preparing aluminum citrate, the method comprising:
mixing an acidic aluminum salt solution and an alkaline solution through first stirring, controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution, and then drying and crushing to obtain alumina hydrate precursor powder;
and carrying out second stirring and mixing on the alumina hydrate precursor powder and the citric acid solution to obtain aluminum citrate.
Optionally, the molar ratio is 0.2-0.3.
Optionally, the temperature of the first stirring and mixing is 30-60 ℃.
Optionally, the speed of the first stirring and mixing is 200 r/min-400 r/min.
Optionally, the drying temperature is 70-100 ℃.
Optionally, the solute of the alkaline solution comprises at least one of: sodium carbonate, sodium hydroxide, sodium bicarbonate, urea; and/or the number of the groups of groups,
the solute of the acidic aluminum salt solution comprises at least one of the following: aluminum chloride, aluminum nitrate, aluminum sulfate.
Optionally, the process parameters of the second stirring and mixing include: the temperature is 60-90 ℃ and the time is 30-60 min.
Optionally, the first stirring and mixing the acidic aluminum salt solution and the alkaline solution, controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution, and then drying and crushing to obtain alumina hydrate precursor powder, which comprises the following steps:
mixing an acidic aluminum salt solution, an alkaline solution and a dispersing agent in a first stirring manner, controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution, and drying and crushing to obtain alumina hydrate precursor powder; wherein,
the dispersant is 0.05 to 0.1 parts by weight based on 1 part by weight of the reaction system mixed by the first stirring.
Optionally, the first stirring and mixing the acidic aluminum salt solution and the alkaline solution, controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution, and then drying and crushing to obtain alumina hydrate precursor powder, which comprises the following steps:
the method comprises the steps of (1) carrying out first stirring and mixing on an acidic aluminum salt solution and an alkaline solution, and controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution to obtain slurry;
washing the slurry, and then drying and crushing to obtain alumina hydrate precursor powder; wherein,
the temperature of the washing medium is 30-60 ℃.
In a second aspect, the present application provides an aluminum citrate prepared by the method according to any one of the embodiments of the first aspect.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the preparation method of the aluminum citrate, provided by the embodiment of the application, the acidic aluminum salt solution and the alkaline solution are subjected to neutralization reaction, and the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution is controlled so as to achieve the pH value required by a neutralization reaction system, so that amorphous nano-active aluminum oxide precursors are separated out, nano-scale crystal grains of the precursors are uniformly and orderly separated out, and the activity of the powder is improved; the precursor reacts with citric acid solution, and aluminum citrate can be synthesized under mild reaction conditions due to higher activity of the alumina precursor, so that the technical problem of higher energy consumption of the existing preparation process of aluminum citrate is solved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a schematic flow chart of a preparation method of aluminum citrate according to an embodiment of the present application.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present application, the terms "include", "comprise", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one (a) or the like refer to any combination of these items, including any combination of single item(s) or plural items (a). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
Unless specifically indicated otherwise, the various raw materials, reagents, instruments, equipment, and the like used in this application are commercially available or may be prepared by existing methods.
In a first aspect, the present application provides a method for preparing aluminum citrate, referring to fig. 1, the method includes:
s1, carrying out first stirring and mixing on an acidic aluminum salt solution and an alkaline solution, controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution, and then drying and crushing to obtain alumina hydrate precursor powder;
according to the preparation method of the aluminum citrate, provided by the embodiment of the application, the acidic aluminum salt solution and the alkaline solution are subjected to neutralization reaction, and the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution is controlled so as to achieve the pH value required by a neutralization reaction system, so that amorphous nano-active aluminum oxide precursors are separated out, nano-scale grains of the precursors are uniformly and orderly separated out, and the activity of the powder is improved. In addition, in general, the first stirred solution is filtered, washed, dried, crushed and sieved in order to ensure purity.
In some embodiments, the molar ratio is from 0.2 to 0.3.
In the embodiment of the application, the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution is controlled to achieve the pH value required by a neutralization reaction system, so that amorphous nanometer active aluminum oxide precursors are separated out, nanometer crystal grains of the precursors are uniformly and orderly separated out, and the activity of the powder is improved. If the molar ratio is too large, the pH value of the reaction system is possibly too low, part of aluminum ions cannot be hydrolyzed and separated out, and solid and liquid phases in the system are not easy to separate; if the molar ratio is too small, the pH of the reaction system may be too high, and the nano-sized crystal grain phase of the precursor may be converted and deactivated. Specifically, the molar ratio may be 0.2, 0.25, 0.3, etc.
In some embodiments, the temperature of the first agitation mixing is from 30 ℃ to 60 ℃.
In the embodiment of the application, the temperature of the first stirring and mixing is controlled to be the synthesis temperature of the neutralization reaction, so that the crystal phase of the nano alumina hydrate is well developed, and the nano crystal grains are evenly and orderly separated out, thereby improving the activity of the product. If the synthesis temperature is too high, the nano alumina hydrate crystal phase can be excessively developed to a certain extent, and the activity is reduced; if the synthesis temperature is too low, the nano alumina hydrate grains are too small to some extent, so that the solid-liquid separation and washing speed are reduced. Specifically, the temperature of the first agitation mixing may be 30 ℃, 40 ℃, 50 ℃, 60 ℃, or the like.
In some embodiments, the first agitation mixing is at a speed of 200r/min to 400r/min.
In the embodiment of the application, the speed of the first stirring and mixing is controlled, so that the grain size of the precursor is uniform, and the product activity is good. If the stirring speed is too high, the grain size of the precursor is reduced to a certain extent, so that the difficulty of solid-liquid separation is increased; if the stirring speed is too small, the reaction process is not uniform to a certain extent, and the grain size of the finished product is not uniform, so that the effect of the reaction in the citric acid is affected. Specifically, the speed of the first agitation mixing may be 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, or the like.
In some embodiments, the drying temperature is 70 ℃ to 100 ℃.
In the embodiment of the application, the drying temperature is controlled, so that the activity of the precursor is ensured. If the drying temperature is too high, the activity of the precursor is reduced, and the conversion rate of the aluminum citrate synthesis process is further reduced; if the drying temperature is too low, the drying process is too long. Specifically, the drying temperature may be 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, or the like.
In some embodiments, the solute of the alkaline solution comprises at least one of: sodium carbonate, sodium hydroxide, sodium bicarbonate, urea; and/or the number of the groups of groups,
the solute of the acidic aluminum salt solution comprises at least one of the following: aluminum chloride, aluminum nitrate, aluminum sulfate.
In the embodiment of the application, at least one of sodium carbonate, sodium hydroxide, sodium bicarbonate and urea is selected as a solute in an alkaline solution, and the alkaline solutes are all pH regulators commonly used in industry, so that a large number of hydroxyl groups can be provided as a system pH regulator on one hand, and the production cost can be reduced on the other hand. At least one of aluminum chloride, aluminum nitrate and aluminum sulfate is selected as a solute in an acidic aluminum salt solution, and the acidic solute is common aluminum salt in industry, so that a high-quality aluminum source can be provided in the reaction process, and the production cost can be reduced. In addition, the above reaction materials are selected to prepare a solution, and in general, the prepared solution is filtered to obtain a filtrate as a reactant in order to ensure purity. As one implementation mode, aluminum chloride hexahydrate and anhydrous sodium carbonate are selected, industrial-grade aluminum chloride hexahydrate is prepared into a solution with the concentration of 500g/L, and the solution is filtered to obtain an aluminum chloride solution; preparing industrial anhydrous sodium carbonate into a solution with the concentration of 250g/L, and filtering to obtain a sodium carbonate solution.
S2, carrying out second stirring and mixing on the alumina hydrate precursor powder and the citric acid solution to obtain aluminum citrate.
In some embodiments, the process parameters of the second agitation mixing include: the temperature is 60-90 ℃ and the time is 30-60 min.
In the embodiment of the application, the process parameters of the second stirring and mixing are controlled to ensure complete reaction, and the precursor reacts with the citric acid solution, so that the aluminum citrate can be synthesized under mild reaction conditions due to higher activity of the aluminum oxide precursor, thereby solving the technical problem of higher energy consumption of the existing preparation process of the aluminum citrate. If the temperature of the synthesized aluminum citrate is too low or the time is too short, the precursor cannot be completely converted into aluminum citrate, and if the temperature of the synthesized aluminum citrate is too high or the time is too long, the production cost is increased. Specifically, the temperature may be 60 ℃, 70 ℃, 80 ℃, 90 ℃, etc., and the time may be 30min, 40min, 50min, 60min, etc. In addition, the citric acid aluminum acid solution is prepared by preparing 500g/L solution from citric acid monohydrate, and in general, the solution is filtered to obtain citric acid solution in order to ensure purity. The weight ratio of the precursor to the citric acid solution in the synthesis process of the aluminum citrate solution is 0.3-0.35.
In some embodiments, the first stirring and mixing the acidic aluminum salt solution and the alkaline solution, controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution, and then drying and crushing to obtain alumina hydrate precursor powder, which comprises the following steps:
mixing an acidic aluminum salt solution, an alkaline solution and a dispersing agent in a first stirring manner, controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution, and drying and crushing to obtain alumina hydrate precursor powder; wherein,
the dispersant is 0.05 to 0.1 parts by weight based on 1 part by weight of the reaction system mixed by the first stirring.
In the examples herein, the action of the dispersant: so that the reactants are uniformly dispersed. The dispersing agent can be water or ethanol, the dosage of the dispersing agent is controlled, the contact area of reactants is increased, and the reaction rate is improved. If the consumption of the dispersing agent is too high, the slurry solid content is possibly too low, and the water consumption is large; if the dosage of the dispersing agent is too low, the system concentration can be too high, which is unfavorable for orderly precipitation of nano grains. Specifically, the dispersant may be 0.05 parts by weight, 0.06 parts by weight, 0.07 parts by weight, 0.08 parts by weight, 0.09 parts by weight, 0.1 parts by weight, and the like, with respect to 1 part by weight of the first stirred and mixed reaction system.
In some embodiments, the first stirring and mixing the acidic aluminum salt solution and the alkaline solution, controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution, and then drying and crushing to obtain alumina hydrate precursor powder, which comprises the following steps:
the method comprises the steps of (1) carrying out first stirring and mixing on an acidic aluminum salt solution and an alkaline solution, and controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution to obtain slurry;
washing the slurry, and then drying and crushing to obtain alumina hydrate precursor powder; wherein,
the temperature of the washing medium is 30-60 ℃.
In the examples herein, the temperature of the wash medium is controlled to ensure purity of the alumina hydrate precursor. If the washing temperature is too high, the precursor crystal phase can be excessively developed to a certain extent; if the washing temperature is too low, the sodium chloride of the system is not easy to remove to a certain extent. Specifically, the temperature of the washing medium may be 30 ℃, 40 ℃, 50 ℃, 60 ℃, or the like. The volume of the washing medium is 1 time or more the volume of the slurry. The washing medium may be ethanol, water.
In a second aspect, the present application provides an aluminum citrate prepared by the method according to any one of the embodiments of the first aspect.
The aluminum citrate obtained by the preparation method of the aluminum citrate provided by the application has high purity, can not contain inorganic salt byproducts, has simple synthesis process and stable product quality; and effectively improve Al in the aluminum citrate solution 3+ Content, improved complexing effect, product Al 3+ The content is more than or equal to 8 weight percent. The aluminum citrate can be used as a cross-linking agent, and is mixed with Polyacrylamide (PAM) to gradually form a reticular gel, so that the aluminum citrate can be used for plugging water and controlling profile of an oil field and plugging a high permeable layer of the oil field.
The aluminum citrate is realized based on the preparation method of aluminum citrate, and specific steps of the preparation method of aluminum citrate can refer to the above embodiment, and because the aluminum citrate adopts part or all of the technical schemes of the above embodiment, the aluminum citrate has at least all the beneficial effects brought by the technical schemes of the above embodiment, and the detailed description is omitted.
The present application is further illustrated below in conjunction with specific examples. It should be understood that these examples are illustrative only of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
(1) Preparing industrial aluminum chloride hexahydrate and industrial anhydrous sodium carbonate into solutions of 500g/L and 250g/L respectively, and filtering to obtain filtrate;
(2) Mixing 1000mL of aluminum chloride solution and 3500mL of sodium carbonate solution under first stirring at 40 ℃, and drying and crushing to obtain alumina hydrate precursor powder; wherein: the first stirring and mixing speed is 300r/min; the molar ratio of aluminum chloride in the aluminum chloride solution to sodium carbonate in the sodium carbonate solution is 0.25, and the drying temperature is 80 ℃;
(3) Preparing industrial grade citric acid monohydrate into 500g/L solution, and filtering to obtain filtrate;
(4) Mixing 120g of precursor with 350g of citric acid solution under second stirring at 80 ℃, and drying to obtain aluminum citrate powder; wherein: the second stirring and mixing time is 40min; the speed of the second stirring was 200r/min.
Example 2
(1) Preparing industrial aluminum chloride hexahydrate and industrial anhydrous sodium carbonate into solutions of 500g/L and 250g/L respectively, and filtering to obtain filtrate;
(2) Mixing 1000mL of aluminum chloride solution, 3500mL of sodium carbonate solution and water at 40 ℃ under first stirring to obtain slurry;
wherein: the first stirring and mixing speed is 300r/min; the volume of water was 300mL; the molar ratio of aluminum chloride in the aluminum chloride solution to sodium carbonate in the sodium carbonate solution is 0.25;
(3) Filtering, washing, drying, crushing and screening the slurry to obtain an active nano alumina hydrate precursor;
wherein: the volume of water used for washing was 5L; the water temperature for washing is 40 ℃; the drying temperature is 80 ℃;
(4) Preparing industrial grade citric acid monohydrate into 500g/L solution, and filtering to obtain filtrate;
(5) Mixing 120g of precursor with 350g of citric acid solution under second stirring at 80 ℃, and drying to obtain aluminum citrate powder; wherein: the second stirring and mixing time is 40min; the speed of the second stirring was 200r/min.
Example 3
The reaction volume of the aluminum chloride solution in example 2 was 1000mL, the reaction volume of the sodium carbonate solution was 3000mL, and the molar ratio of aluminum chloride in the aluminum chloride solution to sodium carbonate in the sodium carbonate solution was set to 0.2, the remainder being the same as in example 2.
Example 4
The reaction volume of the aluminum chloride solution in example 2 was 1000mL, the reaction volume of the sodium carbonate solution was 4000mL, and the molar ratio of aluminum chloride in the aluminum chloride solution to sodium carbonate in the sodium carbonate solution was set to 0.3, the remainder being the same as in example 2.
Comparative example 1
The reaction volume of the aluminum chloride solution in example 2 was 800mL, the reaction volume of the sodium carbonate solution was 3700mL, the molar ratio of aluminum chloride in the aluminum chloride solution to sodium carbonate in the sodium carbonate solution was 0.19, and the remainder was the same as in example 2.
Comparative example 2
The temperature of the first agitation mixture in example 2 was set to 70℃and the rest was the same as in example 2.
Comparative example 3
The water temperature for washing in example 2 was set to 80℃and the rest was the same as in example 2.
Comparative example 4
The temperature of drying in example 2 was set to 120℃and the rest was the same as in example 2.
Comparative example 5
The time of the first agitation mixing in example 2 was set to 20 minutes, and the rest was the same as in example 2.
The aluminum citrate provided in examples 1 to 4 and comparative examples 1 to 5 were subjected to physical and chemical index tests, and the test results are shown in table 1 below.
Table 1 results of physical and chemical index tests on aluminum citrate
By the preparation method of aluminum citrate in the examples of the present application, example 1 did not ensure purity and did not use a dispersing agent, al 3+ The method of the embodiment is adopted in the embodiment 2 to 4, the product quality is stable, the purity of the prepared aluminum citrate is higher than 99.9 percent, the inorganic salt byproducts pollute the environment, and the liquid product Al 3+ The content is more than or equal to 8 weight percent. Comparative examples 1 to 5 are not according to the examples of the present applicationControlling the process parameters to a certain extent so that the final Al 3+ The content is reduced, and the phase is not single.
Comparing with Chinese patent (ZL 001358774), it is proposed that aluminum chloride and sodium aluminate are used as aluminum source, and are complexed with citric acid to obtain Al 3+ Aluminum citrate (liquid) with the content of 3.5-5.5 percent, but hydrogen chloride is generated in the preparation process, so that the environment is polluted. The aluminum citrate synthesized by the process contains a certain amount of sulfate or chloride salt, so that the use effect is affected and the environment is polluted. It is apparent that the process for preparing aluminum citrate of the present application has significant advantages.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for preparing aluminum citrate, the method comprising:
mixing an acidic aluminum salt solution and an alkaline solution through first stirring, controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution, and then drying and crushing to obtain alumina hydrate precursor powder;
and carrying out second stirring and mixing on the alumina hydrate precursor powder and the citric acid solution to obtain aluminum citrate.
2. The method according to claim 1, wherein the molar ratio is 0.2 to 0.3.
3. The method of claim 1, wherein the first agitating mixing temperature is from 30 ℃ to 60 ℃.
4. The method of claim 1, wherein the first agitation mixing is at a speed of 200r/min to 400r/min.
5. The method of claim 1, wherein the drying temperature is 70 ℃ to 100 ℃.
6. The method of any one of claims 1 to 5, wherein the solute of the alkaline solution comprises at least one of: sodium carbonate, sodium hydroxide, sodium bicarbonate, urea; and/or the number of the groups of groups,
the solute of the acidic aluminum salt solution comprises at least one of the following: aluminum chloride, aluminum nitrate, aluminum sulfate.
7. The method of claim 1, wherein the second agitating mixing process parameters comprise: the temperature is 60-90 ℃ and the time is 30-60 min.
8. The method according to claim 1 or 2, wherein the first stirring and mixing of the acidic aluminum salt solution and the alkaline solution are performed, and the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution is controlled, and then drying and pulverizing are performed to obtain the alumina hydrate precursor powder, which comprises:
mixing an acidic aluminum salt solution, an alkaline solution and a dispersing agent in a first stirring manner, controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution, and drying and crushing to obtain alumina hydrate precursor powder; wherein,
the dispersant is 0.05 to 0.1 parts by weight based on 1 part by weight of the reaction system mixed by the first stirring.
9. The method according to claim 1 or 2, wherein the first stirring and mixing of the acidic aluminum salt solution and the alkaline solution are performed, and the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution is controlled, and then drying and pulverizing are performed, so as to obtain alumina hydrate precursor powder, which comprises:
the method comprises the steps of (1) carrying out first stirring and mixing on an acidic aluminum salt solution and an alkaline solution, and controlling the molar ratio of aluminum ions in the acidic aluminum salt solution to solutes in the alkaline solution to obtain slurry;
washing the slurry, and then drying and crushing to obtain alumina hydrate precursor powder; wherein,
the temperature of the washing medium is 30-60 ℃.
10. An aluminium citrate, characterized in that it is prepared by the method according to any one of claims 1 to 9.
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