CN105214739B - Modified Aluminum sol and preparation method thereof - Google Patents
Modified Aluminum sol and preparation method thereof Download PDFInfo
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- CN105214739B CN105214739B CN201410251446.1A CN201410251446A CN105214739B CN 105214739 B CN105214739 B CN 105214739B CN 201410251446 A CN201410251446 A CN 201410251446A CN 105214739 B CN105214739 B CN 105214739B
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Abstract
Modified Aluminum sol and preparation method thereof, in the modified Aluminum sol：A concentration of 49 weight %, Al/Cl weight ratios of 8 13 weight %, Cl concentration of Al are 1.2 2.2：1, Si concentration, 0.1 1 weight %, pH value are 2.2 5.2.The modified Aluminum sol preparation method, including：By metallic aluminium, water and soluble silicon-containing compound chloride hybrid reaction, wherein the metallic aluminium and soluble silicon-containing compound add in before chloride.The modification Aluminum sol has higher active and preferable selectivity, available for preparing catalytic cracking catalyst.
Description
Technical field
The present invention relates to a kind of colloidal sol containing chloride and aluminiums of modification and preparation method thereof, are suitable for urging more specifically to one kind
The modification colloidal sol containing chloride and aluminium preparation method of fluidized cracking catalysts.
Background technology
United States Patent (USP) USP2196016 reports the preparation method of Aluminum sol earliest.At present, Aluminum sol (colloidal sol containing chloride and aluminium,
Be frequently termed as aluminium polychloride as sewage treatment flocculating agent) preparation method have it is following several：It is anti-with metallic aluminium with aluminium chloride
It answers, reacted with freshly prepared aluminium hydroxide with hydrochloric acid and metal reactive aluminum, with metallic aluminium with hydrochloric acid, being passed through by raw material of aluminium chloride
It is prepared by ion exchange or thermal decomposition.
United States Patent (USP) USP3464929 is for the first time by Aluminum sol (referring to colloidal sol containing chloride and aluminium) for catalyst preparation.Due to good
Good adhesive property, Aluminum sol is zeolite catalyst particularly high zeolite content catalyst such as catalytic cracking catalyst at present
Common binding agent.However with existing colloidal sol containing chloride and aluminium be binding agent prepare Cracking catalyst, matrix-active is relatively low, selectivity
It is poor.
Chinese patent ZL91108723.0 (CN1029219C) and Chinese patent ZL91108724.9 (CN1029220C) are carried
The preparation method of modified colloidal sol containing chloride and aluminium has been supplied, a small amount of phosphate radical is introduced in Aluminum sol.However above phosphorated aluminiferous collosol
Hydrocarbon cracking catalyzer prepared by binding agent, activity is relatively low, and reaction selectivity is not high.
Invention content
It is low the technical problem to be solved by the present invention is to be directed to existing Aluminum sol and P Modification Aluminum sol activity, poor selectivity
Problem provides a kind of modified Aluminum sol and preparation method thereof.
The present invention provides a kind of modified Aluminum sol, in the modified Aluminum sol, a concentration of 8-13 weight %, Cl concentration 4- of Al
9 weight %, Al/Cl weight ratios are 1.2-2.2：1, Si concentration 0.1-1 weight %, pH value 2.2-5.2.
The wherein described Al concentration refers to the concentration (or content) of aluminium element in modified Aluminum sol, and Cl concentration refers to chlorine element
Concentration (or content), Si concentration refers to the concentration (or content) of element silicon, and Al/Cl weight ratios refer to aluminium member in modified Aluminum sol
Element and the weight ratio of chlorine element.
The present invention provides a kind of preparation method of the modified Aluminum sol, including：By metallic aluminium, water and soluble silicide-comprising
It closes object and chloride is introduced into reactor and is reacted, wherein soluble silicon-containing compound is added to instead before chloride is added in
It answers in device, Al/Si rate of charges are 10-150:1.
Wherein described chloride includes the chloride of hydrogen chloride and/or aluminium.Wherein described Al/Si rate of charges (also referred to as aluminium silicon
Rate of charge) it is the aluminium element summation of chloride introducing of metallic aluminium and aluminium and the weight of the element silicon of soluble silicon-containing compound introducing
Amount ratio.When the chloride does not include the chloride of aluminium during for example, hydrogen chloride, aluminium element amount that the chloride of aluminium introduces
It is that zero, Al/Si rate of charges are equal to the weight ratio of element silicon that the aluminium element that metallic aluminium introduces is introduced with soluble silicon-containing compound,
It is equal to the metallic aluminium in terms of Al and the soluble silicon-containing compound weight ratio in terms of Si, which is 10-150:1 is, for example, 15
~135:1.When the chloride includes the chloride of aluminium, the Al/Si rate of charges are equal to the aluminium element that metallic aluminium introduces
The weight ratio of element silicon that the sum of aluminium element introduced with the chloride of aluminium is introduced with soluble silicon-containing compound, that is, be equal to Al
The chloride summation of the metallic aluminium of meter and the aluminium in terms of Al and the soluble silicon-containing compound weight ratio in terms of Si, it is preferred that Al/
Si rate of charges are 10-100:1 is, for example, 15-70:1 or 19-60:1.
In modified Aluminum sol preparation method provided by the invention, it is molten that reaction generation aluminium is carried out in the presence of silicon-containing compound
Glue, the silicon-containing compound are soluble silicon-containing compound, and the soluble silicon-containing compound is can be dissolved in water or energy
Enough silicon-containing compounds that (such as hydrolysis occurs) generation Si oxide is reacted with water.The soluble silicon-containing compound example
As one or more in waterglass, acidic silicic acid, alkoxy silane, can be contained by adding in the solubility in mixed process
Silicon compound is in itself or the solution of soluble silicon-containing compound introduces soluble silicon-containing compound.
A kind of embodiment, by add in waterglass, sodium silicate solution, acidic silicic acid aqueous solution, alkoxy silane or
The solubility described in one or more introducings in the organic solvent solution of the solution of alkoxy silane such as alkoxy silane contains
Silicon compound, wherein the organic solvent is preferably the one kind that can be dissolved in organic solvent such as methanol, ethyl alcohol, the acetone of water
It is or a variety of.Wherein, the waterglass, modulus can be that 2.0-3.5 is, for example, 2.6-3.3, can use technical grade ratings above
Waterglass, waterglass can first be made sodium silicate solution and added instead by for example, chemical pure or commercially pure waterglass
It answers in device, SiO in the sodium silicate solution2Concentration is preferably 1-25 weight %；The acidic silicate solution, SiO2It is a concentration of
1-10 weight %, pH value 1.5-3.0；The alkoxy silane, chemical formula are Si (OR)4, wherein R is carbon number less than 10
Unsubstituted or substitution alkyl (alkyl of the substituted base of alkyl of the carbon number less than 10 or carbon number less than 10), same alkoxy silane
Four R in molecule each other can be identical or different；The solution such as ethanol solution of alkoxy silane, the alkane can be added in
Si concentration of element can be 1-10 weight % in the solution of oxysilane.Alkoxy silane can be more than technical grade, such as can
Think that chemical pure or technical grade is pure.The alkoxy silane is for example：Tetraethoxysilane, tetramethoxy-silicane, a methoxyl group
It is one or more in triethoxysilane, dimethoxy diethoxy silane.
In modified Aluminum sol preparation method provided by the invention, can by soluble silicon-containing compound solution, pass through chlorine
Compound solution is introduced by adding in water such as deionized water or combination in the above manner introduces water into reactor, excellent
Choosing, it adds in chloride and is contained with the water being introduced into forward direction reactor with adding in chloride with the solubility introduced in forward direction reactor
The weight ratio of silicon compound (being counted using Si) is 100:0.1-10 is, for example, 100:1-10、100:0.1-5、100:0.15-1.4 or
100:0.2-1.2。
Silicon (in terms of element silicon) concentration is preferably 0.1-1 weight % in the modification Aluminum sol that the present invention obtains, more preferably
0.2-0.9 weight % is, for example, 0.3~0.85 weight %.
In modified Aluminum sol preparation method provided by the invention, reacted using metallic aluminium, metallic aluminium plus people amount (with
Element aluminum meter) can be metallic aluminium consumption in reaction process 100-220%, i.e., plus equivalent or excess metallic aluminium.It is used
Metal aluminum feedstock can be one or more in aluminium ingot, aluminium skimmings or aluminum shot, the content of aluminium is (pure in the metal aluminum feedstock
Degree) it is preferably not less than 95 weight %, for example, 95-99.7 weight %.
In modified Aluminum sol preparation method provided by the invention, the addition of chloride makes the Al/Cl weight ratios of product be
1.2-2.2：1.Under preferable case, Al/Cl rate of charges are 1.2-4.0:1 is, for example, 1.3-3.5:1, the Al/Cl rate of charges are
The aluminium in reactor is introduced into (including the aluminium element that metallic aluminium introduces, if the chloride for adding in aluminium further includes aluminium as chlorine source
The aluminium element that introduces of chloride be aluminium that metallic aluminium introduces and aluminium the sum of aluminium that introduces of chloride) and the chlorine (chlorination
Object introduce chlorine element) weight ratio.The chloride can be one kind in the chloride such as aluminium chloride and hydrogen chloride of aluminium
It is or a variety of.The chloride can be introduced, such as add in hydrochloric acid or liquor alumini chloridi or contain salt by adding in chloride solution
The solution of acid and aluminium chloride, the concentration of chlorine is preferably 15-20 weight % in the chloride solution.When using hydrochloric acid, with chlorine
It is preferably 15-20 weight % to count its concentration；Technical grade can be used with higher level, for example, chemical pure or technical grade.When using chlorine
Change aluminium (AlCl3) solution when, the wherein a concentration of 15-20 weight % of chlorine can be formulated with crystal aluminum chloride and water, knot
Brilliant aluminium chloride can be chemical pure or technical grade.
Metallic aluminium, water and soluble silicon-containing compound are introduced reaction by modified Aluminum sol preparation method provided by the invention
Mixture is formed in device, chloride is then added in into reactor is reacted.Aluminium in modified aluminium sol product obtained by the reaction
The content that concentration reaches aluminium element in the modified Aluminum sol of requirement such as gained is 8-13 weight %, stops reaction.It can be anti-by inciting somebody to action
Product filtering is answered to terminate to react or by the way that product cooling is for example cooled below 80 DEG C preferably shorter than 70 DEG C stop
Reaction, is then filtered to get Si modification Aluminum sol product.It is, for example, 80-102 DEG C that reaction temperature, which is preferably 60-105 DEG C, reaction
Time makes a concentration of 8-13 weight % of aluminium in obtained modified Aluminum sol.Under preferable case, from be initially added into chloride to
It is 60-102 DEG C to terminate to add in the reaction temperature between chlorination, and the addition time of chloride is 1-4 hours preferred for 0.5-4 hours；
Reaction temperature after chloride adds is 80-105 DEG C for example, 90-98 DEG C；Reaction time 12-72 hour is, for example, 16-26
Hour, the reaction time is to be calculated from being initially added into chloride, also referred to as total reaction time.
The modification Aluminum sol that modified Aluminum sol preparation method provided by the invention obtains, can also be concentrated, to improve
The wherein concentration of aluminium, if for example, the aluminum concentration of product can put forward the concentration of aluminium in Aluminum sol less than 10 weight % by concentration
More than height to 10 weight %, the concentration can be concentrated by evaporation, be concentrated by evaporation condition for example：80-105 DEG C of temperature, when
Between can be 0.5-4 hours.Usually the aluminum concentration of product is made to be 10-13 weight % such as 10-12 weight % by concentration.
Siliceous Aluminum sol i.e. Si modification Aluminum sol can be made in modified Aluminum sol preparation method provided by the invention, should
The aluminium polychloride micelle of Si modification is formed in modified Aluminum sol, silicon is evenly distributed, and will not form larger silicon oxide particle,
Silica-alumina gel block will not be formed, there is good adhesive property, matrix-active is higher, can be used as zeolite type crystalline aluminosilicate molecule
Sieve catalyst binding agent, particularly as SiO2/Al2O3Than relatively low crystalline aluminosilicate molecular sieve catalyst binding agent for example
The Cracking catalyst of the zeolite containing Y, prepared catalyst reaction performance are better than colloidal sol containing chloride and aluminium and phosphorated aluminiferous collosol, caking property
With matrix-active better than Alusil catalyst and Ludox catalyst, selectivity is preferably.
Specific embodiment
In modified Aluminum sol provided by the invention, the Al elements containing 8-13 weight % such as 8-12.5 weight %, 4-9 weights
Measure % such as 4.5-9 weight %Cl elements and 0.1-1 weight % preferably 0.3~0.9 weight %Si elements；The modified Aluminum sol
In also contain water, such as the content of water can be 60-80 weight % be, for example, 66-77 weight %, usually contain the water of aequum；
Al/Cl weight ratios are 1.2-2.2:1, Al/Si weight ratio is 9.5-100:1 is, for example, 9.8-90:1 or for 10-80:1 or 10-
50:1, pH value is, for example, 2.5-5.2 for 2.2-5.2:1.
Modified Aluminum sol provided by the invention, a kind of specific embodiment, Al elements, 4.2- containing 8-12.3 weight %
8.8 weight %Cl elements and 0.2-0.9 weight %Si elements；Al/Cl weight ratios are 1.25-2.1:1, Al/Si weight ratio is
9.8-80:1, pH value 2.8-5.2:1；The content of the element silicon is preferably that 0.2~0.9 weight % is, for example, 0.3~0.85
Weight %.
Modified Aluminum sol preparation method provided by the invention, a kind of embodiment first make metallic aluminium, soluble siliceous chemical combination
Object and water form mixture, then add in aqueous chloride solution and are reacted.It is described make metallic aluminium, soluble silicon-containing compound and
In the mixture that water is formed, the weight ratio of the soluble silicon-containing compound and water is counted as 0.1-10 using Si:100 be, for example, 1-
10:100；In the case of more preferably, add in before aqueous chloride solution, in the reactor, the dissolvable silicon-containing compound
The element silicon of introducing and the weight ratio of water (water that water and dissolvable silicon-containing compound aqueous solution including addition introduce) are 0.1-
5:100, for example, 0.1-3:100 or for 0.15-1.4:100, further for example, 0.2-1.3:100.Under preferable case, add in
Before aqueous chloride solution, the temperature of mixture that metallic aluminium, water and soluble silicon-containing compound are mixed to form is made to be not less than 60
DEG C be, for example, 60-102 DEG C, then add in chloride reacted so that add in chloride when with higher reaction temperature.For
Reaction speed is too fast when avoiding adding in a large amount of chlorides causes rapid reaction heat release, temperature quickly raising causes reactant to boil
It rises, chloride can be added in several times or is slowly added to chloride, such as the feed time of chloride can be made at 0.5 hour
More than, it is preferable that the addition time of chloride is (from chloride is initially added into the time or chloride for terminating addition chloride
Feed time) be 1-4 hours.It is preferred that during chlorination compound, the reaction temperature in reactor is no more than 102 DEG C, for example,
60-100℃.Preferably, reaction temperature is 80-105 DEG C, and the reaction time is 12-72 hours；The further reaction time is 90-98
DEG C, the reaction time for 16-26 hour (reaction temperature and reaction time refer to from be initially added into chloride solution calculating).
Modified Aluminum sol preparation method provided by the invention, the first specific embodiment include the following steps：
(1) metal silicon source, soluble silicon-containing compound silicon source and water are added in reactor, are wherein obtained in reactor
Mixture temperature not less than 60 DEG C be, for example, 60-102 DEG C, can by by obtained low-temperature mixed object heat or pass through
The higher raw material of temperature is mixed to the temperature for reaching described；The dosage of water makes to introduce by soluble silicon-containing compound in reactor
The weight ratio of element silicon and water (water that water and soluble silicon-containing compound silicon source including addition introduce) be 0.1-10:100
For example, 1-10:100 or for 0.1-5:100 or for 0.05-1.5:100 or for 0.1-1.4:100 or for 0.15-1.3:100；With
Al counts metal silicon source with counting the weight ratio of soluble silicon-containing compound as 10-150 using Si:1 i.e. Al/Si rate of charges are 10-150:1
For example, 15~100:1 or for 19~60:1；It is one or more in the metal silicon source such as aluminium ingot, aluminum shot, aluminium powder；Institute
It is, for example, waterglass solid, water glass solution, acidic oxidation silicon aqueous solution, alkoxy silane to state soluble silicon-containing compound silicon source
It is and one or more in alkoxy silane solution；
(2) hydrochloric acid is added in the mixture obtained in step (1), a concentration of 15-20 weight % of the hydrochloric acid in terms of chlorine；
It is, for example, 1.5-3 hours that the addition time of hydrochloric acid, which is preferably 1-4 hours,；The temperature of mixture is 60-102 DEG C in reactor；Al/
Cl rate of charges (weight ratio for being equal to the metallic aluminium and the hydrochloric acid in terms of chlorine in terms of aluminium in present embodiment) are 1.2-4:1；
(3) mixture that step (2) obtains is reacted at 80-105 DEG C preferably 90-98 DEG C, what the reaction time made
A concentration of 8-13 weight % of Al in Aluminum sol；Preferably, step (3) reaction time is such as 14-25 hours 8-71 hours；From
It is preferably more preferably 16-26 hours 12-71 hours that step (2), which is initially added into hydrochloric acid and rises to the total reaction time of reaction terminating,.
Reaction is terminated by filtering or cooling down and then filtering product obtained by the reaction, obtains Si modification Aluminum sol；The cooling makes cold
But the reaction product temperature after is less than 80 DEG C, preferably shorter than 70 DEG C, for example, -70 DEG C of room temperature, and room temperature is 15-40 DEG C.It is usually cold
But to 60-70 DEG C.
Modified Aluminum sol preparation method provided by the invention, second of specific embodiment include the following steps：
(1) metal silicon source, soluble silicon-containing compound silicon source, water are added in reactor and form mixture, wherein institute
The temperature of obtained mixture is, for example, 60-100 DEG C not less than 60 DEG C；Can by the heating of the low-temperature mixed object that will obtain or
By the way that the higher raw material of temperature is mixed the temperature for reaching described；One in the metal silicon source such as aluminium ingot, aluminum shot, aluminium powder
Kind is a variety of；The solubility silicon-containing compound silicon source is, for example, waterglass, water glass solution, acidic oxidation silicon solution, alcoxyl
It is one or more in base silane and alkoxy silane solution；It is introduced in mixture by soluble silicon-containing compound silicon source
The weight ratio of element silicon and water (water that water and soluble silicon-containing compound silicon source including addition introduce) is no more than 10:100
Such as it is 0.1-10:100 or for 1-10:100 or for 0.1-5:100 or for 0.15-1.5:100 or for 0.2-1.3:100；Al/Si
Rate of charge is 10-150:1 is, for example, 15~100:1 or for 19~60:1, wherein the Al/Si rate of charges draw equal to metallic aluminium
The sum of aluminium element that the solution of chloride containing aluminium introduces in the aluminium element and step (2) that enter is introduced with soluble silicon-containing compound silicon source
Element silicon weight ratio；
(2) solution of chloride containing aluminium is added in the mixture obtained in step (1), the solution of the chloride containing aluminium includes
The chloride of aluminium, with or without there is hydrochloric acid；The solution of the chloride containing aluminium can be that liquor alumini chloridi or hydrochloric acid and aluminium chloride mix
Close the solution formed.The concentration of the Chlorine in Solution of the chloride containing aluminium is preferably 15-20 weight %, the solution of the chloride containing aluminium
The addition time be preferably 1-4 hours, for example, 1.5-3 hours；
(3) mixture that step (2) obtains at 80-105 DEG C preferably 90-98 DEG C is reacted, then terminates reaction；Al/
Cl rate of charges (are equal to the solution introducing of aluminium element and chloride containing aluminium that metallic aluminium introduces in this second of specific embodiment
The sum of aluminium element and chloride containing aluminium the weight ratio of chlorine element that introduces of solution) be 1.2-4:1.The aluminium that reaction time makes
A concentration of 8-13 weight % of Al in colloidal sol, the reaction time of step (3) preferably are 12-25 hours more preferable for 8-71 hours；
The total reaction time started from the chloride for being initially added into aluminium is 12-72 hours preferred, 16-26 hours more preferable.It can be by that will walk
Suddenly the product filtering or cool down, filtering termination reaction that (3) obtain, obtain Si modification Aluminum sol；It is cooled below 80 DEG C, it is excellent
Choosing is less than 70 DEG C, and for example, -70 DEG C of room temperature, room temperature are 15-40 DEG C.
The present invention is further described for the following examples, but not thereby limiting the invention.
99.2 weight % of aluminium skimmings purity used in embodiment, aluminum shot purity are 98.8 weight %.
Embodiment 1
By aluminium skimmings 280 grams (in terms of Al), 1481 grams of deionized water and sodium silicate solution (9.33 weight % of element containing Si,
4.63 weight % of Na elements) 119 grams be put into there-necked flask, be heated to 60 DEG C.By 1:1 chemical pure hydrochloric acid is (by the concentration of 1 volume
Water for 36 weight % chemistry pure hydrochloric acids and 1 volume mixes) 921 milliliters be slowly added in there-necked flask, during the addition of hydrochloric acid
Between be 3 hours；After adding hydrochloric acid, reacted 20 hours at 90-95 DEG C of reaction temperature, product is then cooled to 60-70 DEG C, mistake
Filter obtains modified Aluminum sol.The weighed aluminium skimmings for reacting remaining are 36 grams, i.e. the excessive 14.8 heavy % of aluminium.Modified aluminium sol product
It is as a result as follows through analysis：9.0 weight %, Cl content of Al content, 6.7 weight %, Si content, 0.41 weight %, Al/Cl (weight
Than) 1.34:1, Al/Si (weight ratio) 22.0:1, pH value 3.00.
Embodiment 2
Aluminium skimmings 280 grams (in terms of Al), 1055 grams of deionized water, sodium silicate solution (%, the Na4.63 weight of weight containing Si9.33
Measure %) 115 grams, it is put into there-necked flask, is heated to 60 DEG C.By 1:1 chemical 678 milliliters of pure hydrochloric acid is slowly added in there-necked flask, salt
The addition time of acid is 3 hours；Then reaction temperature is controlled at such as 90-95 DEG C, reacted 19 hours；Product is cooled to 60-
70 DEG C, filtering.The weighed remaining aluminium skimmings of reaction are 29 grams, i.e. aluminium excessive 11.6%, and product is as follows through analysis result：Al content
12.20 weight %, Cl content, 6.5 weight %, Si content 0.52 heavy %, Al/Cl (weight ratio) 1.88:1, Al/Si (weight ratio)
23.5:1, pH value 4.00.
Embodiment 3
Aluminum shot 250 grams (in terms of Al), 1560 grams of deionized water, tetraethoxysilane ethanol solution (the weight % containing Si3.0)
It 162 grams, adds in three-necked flask bottle, is heated to 60 DEG C；By 1：1 524 milliliters of chemical pure hydrochloric acid is slowly added in there-necked flask, salt
Sour feed time is 2 hours；Reaction temperature is controlled at 93-97 DEG C, is reacted 68 hours；Product is cooled to 60-70 DEG C, mistake
Filter.The weighed remaining aluminum shot of reaction is 48 grams, i.e. the excessive 23.8 heavy % of aluminium.Product has consisting of through analysis：Al content 8.4
4.3 weight %, Si content of weight %, Cl content, 0.20 weight %, Al/Cl (weight ratio) 1.95:1, Al/Si (weight ratio)
42.0:1, pH value 3.8.
Embodiment 4
Aluminum shot 350 grams (in terms of Al), 1190 grams of deionized water, acidic silicic acid aqueous solution (% of weight containing Si5.0, pH value
2.0) it 356 grams, puts in people's there-necked flask, is heated to 60 DEG C.By 1:1 496 milliliters of chemical pure hydrochloric acid is slowly added in there-necked flask, with
Aluminum shot reacts, and the feed time of hydrochloric acid is 2 hours；Reaction temperature control is reacted 18 hours at 93-97 DEG C after adding acid；It will production
Object is cooled to 60-70 DEG C, filtering.The remaining aluminum shot of reaction is 176 grams, i.e., aluminium is excessively 101.1 heavy %.Product contains through analysis
Al8.0 weight %, Cl4.5 weight %, Si0.82 weight %, Al/Cl (weight ratio) are 1.78:1, Al/Si (weight ratio) be
9.8:1, pH value 5.1.
Embodiment 5
Aluminum shot 350 grams (in terms of Al), 1510 grams of deionized water and sodium silicate solution (% of weight containing Si9.33,
Na4.63 weight %) 28 grams, it is put into there-necked flask, is heated to 60 DEG C.By 1：1 488 milliliters of chemical pure hydrochloric acid is slowly added to three
It in mouth bottle, is reacted with aluminum shot, the addition time of hydrochloric acid is 2 hours；Then reaction temperature is controlled at 93-97 DEG C, reaction 24 is small
When；Product is cooled to 60-70 DEG C, filtering.The weighed aluminum shot for reacting remaining is 149 grams, i.e. aluminium excessive 74.1%.Modified aluminium
Sol product is 2.09 containing Al9.2 weight %, Cl4.4 weight %, Si0.12 weight %, Al/Cl (weight ratio) through analysis:
1, Al/Si (weight ratio) is 76.7:1, pH value 3.80.
Embodiment 6
Aluminum shot 250 grams (in terms of Al), 840 grams of deionized water, sodium silicate solution (%, the Na4.63 weight of weight containing Si9.33
Amount %) 63 grams put in people's there-necked flask, be heated to 60 DEG C；By 1:1 829 milliliters of chemical pure hydrochloric acid is slowly added in there-necked flask, salt
The addition time of acid is 3 hours；Then it is 95-100 DEG C in reaction temperature, reacts 17 hours；Reaction product is cooled to 60-70
DEG C, filtering.To reaction, remaining aluminum shot is weighed, and obtains 39 grams, i.e. aluminium is excessively 18.5 heavy %.Product contains through analysis
Al11.1 weight %, Cl8.6 weight %, Si0.31 weight %, Al/Cl (weight) are 1.29:1, Al/Si (weight) is 35.8:
1, pH value 2.9.
Embodiment 7
According to the method for embodiment 2, unlike with aluminum chloride aqueous solution replace hydrochloric acid solution, the chlorine used compared with hydrochloric acid
Change aluminum water solution cl concn is constant, and Al/Cl rate of charges are constant, and Al/Si rate of charges are constant, the corresponding dosage for reducing metallic aluminium.
The modified aluminium collosol concentration arrived is as follows：12.0 weight %, Cl content of Al content, 6.4 weight %, Si content 0.51 heavy %, Al/Cl
(weight ratio) 1.88:1, Al/Si (weight ratio) 23.5:1, pH value 3.90.
Embodiment 8
According to the method for embodiment 6, unlike, with the mixed solution of aluminium chloride and hydrochloric acid (chlorine that aluminium chloride provides and
The ratio for the chlorine that hydrochloric acid provides is 1:1, total cl concn is by 20 weight %) replace the hydrochloric acid solution of embodiment 6.Obtained modified aluminium is molten
Gum concentration is as follows：It is 1.29 containing Al11.0 weight %, Cl8.5 weight %, Si0.31 weight %, Al/Cl (weight):1, Al/
Si (weight) is 35.5:1, pH value 2.90.
Comparative example 1
It is reacted according to existing method using aluminium skimmings with hydrochloric acid and prepares Aluminum sol.
Aluminium skimmings 240 grams (in terms of Al), 1160 grams of deionized water, are put into there-necked flask, are heated to 60 DEG C.By 1:1 chemistry is pure
640 milliliters of hydrochloric acid is slowly added in there-necked flask, makes to react with aluminium skimmings, and the addition time of hydrochloric acid is 3 hours；Then by reaction temperature
Control is reacted 19 hours at such as 90-95 DEG C；Product is cooled to 60-70 DEG C.Product is as follows through analysis result：Al content 12.0
6.3 weight %, Al/Cl (weight ratio) 1.90 of weight %, Cl content:1, pH value 3.40.
CATALYST PREPARATION Comparative's example 1
Kaolin and water are beaten, prepare the kaolin slurry % that solid content is 40 weight, (rare earth contains by REY molecular sieves
Measure 4.3 weight %, silica alumina ratio (SiO2/Al2O3Molar ratio) it is 5.2,0.5 weight % of sodium oxide content) it is beaten with water, it prepares solid
The REY molecular sieve pulps of 40 weight % of content：Kaolin slurry and REY points are sequentially added in the Aluminum sol prepared in comparative example 1
Sub- screening the pulp liquid is beaten, spray drying, and 450 DEG C roast 1 hour, obtain Cracking catalyst, are denoted as DB1.The property of DB1 is shown in Table 1.
Wherein kaolin (in terms of butt):REY molecular sieves (in terms of butt):Aluminum sol (counts) weight ratio as 48 using aluminium oxide:35:17.
CATALYST PREPARATION Comparative's example 2
Waterglass is added in (containing Si9.33 weights according to the ratio of Al/Si=24.1 in the Aluminum sol slurries prepared in comparative example 1
Measure %, Na4.63 weight %) solution, it stirs evenly, then sequentially adds kaolin slurry (reference catalyst prepares comparative example 1)
It with REY molecular sieve pulps (reference catalyst prepares comparative example 1), is beaten, spray drying, 450 DEG C roast 1 hour, obtain cracking
Catalyst is denoted as DB2.Wherein kaolin (in terms of butt):REY molecular sieves (in terms of butt):Aluminum sol (in terms of aluminium oxide) weight
Amount is than being 48:35:17.DB2 properties are shown in Table 1.
Catalyst Preparation Example 1
The modification Aluminum sol prepared with embodiment 2 replaces the Aluminum sol system that comparative example 1 used in preparation comparative example 1 obtains
Standby Cracking catalyst.
Kaolin and water are beaten, prepare the kaolin slurry % that solid content is 40 weight, (rare earth contains by REY molecular sieves
Measure 4.3 weight %, silica alumina ratio (SiO2/Al2O3Molar ratio) it is 5.2,0.5 weight % of sodium oxide content) it is beaten with water, it prepares solid
The REY molecular sieve pulps of 40 weight % of content：Embodiment 2 prepare modification Aluminum sol in sequentially add kaolin slurry and
REY molecular sieve pulps are beaten, spray drying, and 450 DEG C roast 1 hour, obtain Cracking catalyst, are denoted as C1.The property of C1 is shown in Table
1.Wherein, kaolin (in terms of butt):REY molecular sieves (in terms of butt):Modified Aluminum sol (counts) weight ratio as 48 using aluminium oxide:
35:17。
Catalyst Preparation Example 2-5
The modification Aluminum sol prepared with embodiment 4,5,6 and 7 replaces the Aluminum sol in CATALYST PREPARATION Comparative's example 1.It obtains
Catalyst C2, C3, C4 and C5, wherein, kaolin (in terms of butt):REY molecular sieves (in terms of butt):Modified Aluminum sol is (with oxygen
Change aluminium meter) weight ratio is 48:35:17.
Catalyst characterization
Catalyst C1-C5, DB1, DB2 obtained are characterized.Wherein, pore volume is measured using water droplet method, sees Q/
SH349907 methods, abrasion index use Q/SH349909 methods.Characterization result is shown in Table 1.
Catalyst reaction evaluation method
Respectively by catalytic cracking catalyst C1-C5, DB1 and DB2 of above-mentioned preparation, in 800 DEG C, the item of 100% water vapour
Aging 12 hours under part are filled in small fixed flowing bed ACE devices (purchased from KTI companies of the U.S.), amount of fill respectively later
Respectively 9g.Then, reaction temperature be 510 DEG C, weight (hourly) space velocity (WHSV) 12h-1, oil ratio (weight) is under conditions of 6, respectively will
Feedstock oil injection shown in table 2 is filled with the fixed fluidized bed ACE of described aged catalyst Cracking catalyst C1-C5, DB1 and DB2
Catalytic cracking reaction is carried out in device.The composition of reaction product is analyzed, and conversion ratio is calculated according to the following formula, as a result such as table
Shown in 1：
By table 1 as it can be seen that modified Aluminum sol provided by the invention is used to prepare Cracking catalyst, can have it is higher activity and
Relatively low coke selectivity has higher yield of gasoline.
Table 1
Table 2
| Density (20 DEG C)/(kg/m3) | 922.1 |
| Condensation point/DEG C | 33 |
| Carbon residue/% | 3.66 |
| Four component compositions/% | |
| Saturated hydrocarbons | 53.3 |
| Aromatic hydrocarbons | 31.5 |
| Colloid | 14.5 |
| Asphalitine | 0.7 |
| Element composition/% | |
| C | 86.51 |
| H | 12.72 |
| S | 0.35 |
| N | 0.18 |
| Tenor/(μ g/g) | |
| Fe | 6.9 |
| Ni | 10.7 |
| V | 6.5 |
| Na | 0.1 |
| Ca | 1.7 |
Claims (16)
1. a kind of modified Aluminum sol, which is characterized in that in the modified Aluminum sol, a concentration of 8-13 weight %, Cl concentration 4-9 of Al
Weight %, Al/Cl weight ratio are 1. 2-2.2:1, Si concentration 0.1-1 weight %, pH value 2.2-5.2；The modified Aluminum sol
Preparation method, including：Metallic aluminium, water and soluble silicon-containing compound and chloride are added to reactor and reacted, institute
Chloride is stated as hydrogen chloride and/or the chloride of aluminium, wherein, metallic aluminium and soluble silicon-containing compound are before chloride addition
It adds in, aluminium silicon rate of charge is 10-150:1, the aluminium element summation that the aluminium silicon rate of charge is introduced for the chloride of metallic aluminium and aluminium
The weight ratio of the element silicon introduced with soluble silicon-containing compound.
2. modified Aluminum sol described in accordance with the claim 1, which is characterized in that the modified aluminium Sol A l/Si weight ratios are
9.5-100:1。
3. modified Aluminum sol preparation method described in a kind of claim 1, including：By metallic aluminium, water and soluble silicon-containing compound
And chloride is added to reactor and is reacted, wherein, metallic aluminium and soluble silicon-containing compound are before chloride addition
It adds in, aluminium silicon rate of charge is 10-150:1, the aluminium element summation that the aluminium silicon rate of charge is introduced for the chloride of metallic aluminium and aluminium
The weight ratio of the element silicon introduced with soluble silicon-containing compound.
4. modified Aluminum sol preparation method described in accordance with the claim 3, which is characterized in that before adding in chloride, in reactor
The element silicon and the weight ratio of water that the solubility silicon-containing compound introduces are 0.1-10:100, aluminium silicon rate of charge is 15 ~ 100:
1。
5. according to the modification Aluminum sol preparation method described in claim 3 or 4, which is characterized in that before adding in chloride, by metal
Aluminium, water and soluble silicon-containing compound are added in reactor, and in the mixture of formation, the solubility silicon-containing compound introduces
Element silicon and water weight ratio be 0.1-5:100.
6. modified Aluminum sol preparation method described in accordance with the claim 3, which is characterized in that by adding in waterglass solid, water
One or more introducings in glass aqueous solution, acidic silicic acid aqueous solution, alkoxy silane, alkoxy silane solution are described solvable
Property silicon-containing compound.
7. modified Aluminum sol preparation method described in accordance with the claim 3, which is characterized in that the addition of metallic aluminium is metallic aluminium
The 100-220 weight % of consumption.
8. modified Aluminum sol preparation method described in accordance with the claim 3, which is characterized in that Al/Cl rate of charges are 1.2-4:1,
Al/Cl rate of charges are the aluminium being introduced into reactor and the weight ratio of chlorine.
9. according to the modification Aluminum sol preparation method described in claim 3,4,6,7 or 8, which is characterized in that the chloride with
The form of aqueous solution adds in, a concentration of 15-20 weight % of the chloride in terms of chlorine.
10. modified Aluminum sol preparation method described in accordance with the claim 3, which is characterized in that the reaction temperature of reaction is 60-
105℃。
11. modified Aluminum sol preparation method described in accordance with the claim 3, which is characterized in that the reaction temperature of reaction is 80-
105 DEG C, the reaction time is 12-72 hours.
12. according to the modification Aluminum sol preparation method described in claim 11, which is characterized in that the reaction temperature of the reaction is
90-98 DEG C, the reaction time is 16-26 hours.
13. modified Aluminum sol preparation method described in accordance with the claim 3, which is characterized in that the addition time of chloride solution
To be more than 0.5 hour.
14. modified Aluminum sol preparation method described in accordance with the claim 3, which is characterized in that aluminium silicon rate of charge 19 ~ 60:1.
15. according to the modification Aluminum sol preparation method described in claim 5, which is characterized in that the solubility silicon-containing compound draws
The element silicon and the weight ratio of water entered is 0.2-1.3:1.
16. modified Aluminum sol preparation method described in accordance with the claim 3, which is characterized in that the addition time of chloride solution
It is 1-4 hours.
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