CN109833857A - A kind of preparation method of olefin catalytic carrier silica gel - Google Patents
A kind of preparation method of olefin catalytic carrier silica gel Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of olefin catalytic carrier silica gel, the carrier silica gel is that the synthesis of silica solution is completed using silicate and inorganic acid cocurrent adding manner using silicate as bottom liquid；The aqueous solution cocurrent of the ethanol water of alkali carbonate and two kinds of nitric acid metal salts is added to the synthesis for completing hydrotalcite simultaneously.The technique can increase substantially the specific surface area of silica gel in the case where not influencing the Kong Rong of silica gel, to improve the basic physical properties of carrier silica gel；Technique preparation manipulation is simple, reproducible, and low energy consumption, provides technical support to commercial plant production.
Description
Technical field
The present invention relates to a kind of preparation methods of carrier silica gel, and in particular to a kind of preparation of olefin catalytic carrier silica gel
Method.
Background technique
As catalyst carrier, for silica gel in the case where having suitable Kong Rong, aperture and distribution, high-specific surface area can
Greatly improve catalyst activity.It is more to sacrifice hole to obtain high-specific surface area when traditional method prepares carrier silica gel
Appearance and aperture size size, therefore, it is necessary to meet the preparation process requirement of carriers for catalysts silica gel using new method.Water
Talcum is the double-metal hydroxide of stratiform, and laminate is made of magnesium octahedron and alumina octahedral.The hydrotalcite that do not calcine compares table
Area is in 5~20m2/ g, hydrotalcite specific surface area with higher after calcining, specific surface area is in 200~300m2/ g, calcining front and back
The increase of specific surface area presentation geometry quantity.Because hydrotalcite have unique architectural characteristic, so as to as basic catalyst,
Oxidation reduction catalyst and catalyst carrier.Therefore, hydrotalcite can be used to be modified carrier silica gel, to improve carrier silicon
The specific surface area of glue.
Carrier silica gel is mainly used in traditional Ziegler-Natta catalyst and metallocene calalyst for polymerization of olefine.At present
The preparation method of carrier silica gel has many reports both at home and abroad, such as using silicate as mother liquor, add silicate and inorganic acid into
Row reaction；Or using silicate and inorganic acid as mother liquor, inorganic acid is added and adjusts its pH value；It, will or by the way of cocurrent
Silicate and inorganic acid are added simultaneously to be reacted.
US.5372983 patent disclosure prepares SiO using azeotropic distillation method2.Silicate and dilute sulfuric acid reaction first prepares water
Gel removes impurity through washing, and the alcohol that C5~C6 is then added is steamed such as amylalcohol, hexanol or their mixture by azeotropic
It evaporates, removes the moisture content in hydrogel hole, obtain xerogel.450 DEG C~700 DEG C roast obtained product SiO2.Physical index: Kong Rong
2.2cm3/ g~2.5cm3/ g, specific surface area 420m2/ g~550m2/ g, heap density 0.18g/cm3~2.5g/cm3。
The method that US.5599762,5576262 patents improve its azeotropic distillation.It mainly finds some suitable organic
Compound, such as the compound of alcohol ether, alcohol ether-ether etc, including: ethyoxyl ethyl acetate, tert-butoxy propyl alcohol, methoxyl group
Propyl acetate, n-butoxy propanol and ethoxyl ethyl propionate etc..Work boiling distillation is carried out using these organic compounds, is not only passed through
Ji effectively, and improves the performance of polyethylene catalysts.Improve azeotropic distillation technology, worth carrier S iO2And catalyst performance
It can are as follows: SiO2Specific surface area 520m2/ g~530m2/ g, Kong Rongwei 2.4cm3/ g~2.6cm3/ g, product melt index are
6.5g/10min~6.5g/10min, catalyst activity 7000PEg/gcat.h~8000PEg/gcat.h.
US.3959174 patent discloses the SiO of preparation large specific surface area and Kong Rong2Method.It is main during the preparation process
Reduce SiO2The auxiliary agent of solubility or solvation, so that SiO2In the hydrosol system of preparation, reduces the solubility of SiO2 and analyse
Out at hydrogel, then through aging, washing, drying and roasting preparation SiO2.Described auxiliary agent is ammonia, monohydric alcohol, dihydric alcohol, ketone
And salt.They can reduce the dielectric constant in hydrosol system, to make SiO2Gel is precipitated into.SiO2Physical index: compare table
Area 300m2/ g~450m2/ g, Kong Rongwei 1.2cm3/ g~2.8cm3/g。
The oil company Phillips also discloses many patents, US.4081407,4152503,3099457,3948806,
4436883,4246139 etc., discuss azeotropic distillation technology, it is intended to when solving to remove moisture content from hydrogel, avoid the receipts in hole
It contracts and collapses problem.In addition the method for organic solvent displacement water removal has also been attempted.
Above method is with the obvious advantage, disadvantage there is also.Azeotropic distillation method, has that the distillation water removal time is long, and solvent is expensive, energy
Consume the problems such as big；Organic solvent displacement method, there are the disadvantages of complex for operation step, solvent-oil ratio is big, and recycling is difficult.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing olefin catalytic carrier silica gel, the hole of silica gel holds and aperture is big
Small to be suitable for, specific surface area is largely increased.
For this purpose, the present invention provides a kind of preparation method of olefin catalytic carrier silica gel, it is with silicate, inorganic acid for original
Material, preparation process are as follows:
1) using the aqueous solution of silicate as bottom liquid；
2) aqueous silicate solution and inorganic acid aqueous solution is added in cocurrent, while the ethanol water of alkali carbonate is added in cocurrent
The mixed aqueous solution of solution and two kinds of nitric acid metal salts；
3) adjustment reacting solution pH value is 10~12；
4) volume ratio of the organic alcohol solution of addition inorganic acid, Organic Alcohol and water is 1:5~1:30, adjusts reaction solution
PH value is 9~10；
5) in 70~100 DEG C of hydro-thermal reactions；
6) silica gel product is obtained after acidified, washing, dry, activation.
Specifically, the preparation method of carrier silica gel of the present invention is:
It 1) is that 1.0~3.0mol/L aqueous silicate solution is added in reaction kettle by 30ml~60ml concentration, under stirring condition
It is warming up to 40 DEG C~60 DEG C；
2) 1.0~3.0mol/L aqueous silicate solution and 1.0~3.0mol/L inorganic acid aqueous solution, flow velocity control is added in cocurrent
System is in 3~6ml/min, while the ethanol water and matter for the alkali carbonate that mass fraction is 3%~10% is added in cocurrent
10~the 30ml of mixed aqueous solution for two kinds of nitric acid metal salts that score is 2%~8% is measured, flow control is in 4~7ml/min；Alkali
The volume ratio of ethyl alcohol and water is 1:1~1:10, preferably 1:5~1:9 in the ethanol water of metal carbonate；
3) when reacting solution pH value reaches 10~12, stop that above-mentioned mixed solution, 1.0~2.5h of isothermal reaction is added；
4) organic alcohol solution for the inorganic acid that concentration is 1.0~3.0mol/L is added, flow control in 4~9ml/min,
The volume ratio of Organic Alcohol and water is 1:5~1:30, preferably 1:10~1:20, and adjustment solution ph is 9~10, isothermal reaction 1.0
~2.5h；
5) 3.0~5.0h of hydro-thermal reaction under the conditions of 70~100 DEG C；
6) inorganic acid aqueous solution of 1.0~3.0mol/L is added after reaction, adjustment solution ph is 3~6, reactant
System is down to room temperature, is washed using distilled water or distilled water and alcohol mixeding liquid, then dry at 300~335 DEG C, then in inertia
3.0h~6.0h is activated when gas condition, 400~600 DEG C of temperature, and carrier silica gel is made.
Silicate of the present invention is selected from one or more of sodium metasilicate, potassium silicate, waterglass, the preferably described silicate
The concentration of aqueous solution is 1.0~1.5mol/L.
The inorganic acid is selected from one or more of sulfuric acid, hydrochloric acid, nitric acid, the concentration of the preferably described inorganic acid aqueous solution
For 1.0~1.3mol/L.
Alkali carbonate of the present invention is selected from one or more of potassium carbonate, sodium carbonate, and preferred mass score is
4%~7%.
Described two nitric acid metal salts are selected from magnesium nitrate, aluminum nitrate, nickel nitrate, manganese nitrate, cobalt nitrate, chromic nitrate, nitric acid
Two kinds in terbium, cerous nitrate, the preferably mixing of magnesium nitrate and aluminum nitrate or the mixing of zinc nitrate and aluminum nitrate, two of them nitre
The molar ratio of hydrochlorate is 1:1~1:2, preferably 1:1~1:1.5.
The Organic Alcohol be selected from n-butanol, isobutanol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 1- amylalcohol,
2- amylalcohol, 3- amylalcohol, 2-methyl-1-butene alcohol, 2- methyl -2- butanol, 3- methyl -2- butanol, 3- methyl-1-butanol, 2,2- bis-
At least one of methyl-1-propyl alcohol, preferably n-butanol, 1,3-BDO.
The present invention prepares carrier silica gel using sol gel reaction, using silicate as bottom liquid, using silicate and inorganic acid
The synthesis of cocurrent adding manner completion silica solution；Simultaneously by the ethanol water of alkali carbonate and two kinds of nitric acid metal salts
The synthesis for completing hydrotalcite is added in aqueous solution cocurrent.It can ensure that two kinds of particles are completed sufficiently to connect from precursor using this technique
Touching, with growing up for silica sol particle, hydrotalcite particle is thoroughly dispersed in silica solution network, thus not influencing carrier silica gel
The increase to silica gel specific surface area is completed under the premise of performance.Pass through the organic alcohol solution tune of addition inorganic acid when gel reaction
Reacting solution pH value is saved, and completes the preparation of silica gel by high temperature hydro-thermal reaction.The hydrotalcite of dual-layer face can increase substantially
The specific surface area of carrier silica gel, when reason is that talcum is heated, interlayer constantly removes CO2And water, ordered lamellar structure are destroyed,
Surface area increases, hole Rong Zengjia.Ethyl alcohol is added to preferably be precipitated hydrotalcite in the process, and the addition of Organic Alcohol be for
The hole for improving silica gel holds and distribution.The technique can increase substantially silica gel in the case where not influencing the Kong Rong of silica gel
Specific surface area, to improve the basic physical properties of carrier silica gel；Technique preparation manipulation is simple, reproducible, and low energy consumption, gives industry dress
It sets production and provides technical support.
Specific embodiment
It is further described and proves by the following examples technical effect of the present invention, but should not be understood as to this
The limitation of invention.
Index of correlation is tested in embodiment as follows:
Specific surface area: the test of gas absorption BET method, GB/T19587-2004.
The test of Kong Rong: BJH (Barrett-Joyner-Halenda) method, ISO15901-2.
Average pore size d=4V/A, A are specific surface areas, and V is Kong Rong, and d is aperture.
Embodiment 1
It is that 1.2mol/L sodium silicate solution is added in reaction kettle by 50ml concentration, opens stirring, be warming up to 50 DEG C.With
The aqueous sulfuric acid of 1.1mol/L sodium silicate aqueous solution and 1.25mol/L is added in 4ml/min flow velocity cocurrent, while with 5ml/min
The ethanol water (ethyl alcohol and water volume ratio are 1:6) that mass fraction is 6% sodium carbonate is added in cocurrent and mass fraction is 4%
Magnesium nitrate and aluminum nitrate mixed aqueous solution (two kinds of nitrate molar ratios are 1:1) 25ml, when solution ph reaches 11 in reaction kettle
When, stop that above-mentioned mixed solution, isothermal reaction 2.0h is added.With 6ml/min flow velocity be added concentration for 1.0mol/L sulfuric acid just
Butanol aqueous solution (n-butanol is 1:15 with water volume ratio), stops that sulfuric acid butanol solution is added when solution ph is 9, constant temperature is anti-
Answer 2.0h.Reaction system is warming up to 85 DEG C, isothermal reaction 5.0h.Addition concentration is 1.0mol/L aqueous sulfuric acid, works as solution
Stop being added when pH value is 4.It is cooled to room temperature, respectively three times through the washing of distilled water, distilled water and alcohol mixeding liquid, then exists
It is dry at 335 DEG C, later under inert gas protection, is activated 4 hours at 600 DEG C and obtain carrier silica gel product.Test result is such as
Shown in table 1.
Embodiment 2
Preparation process is with embodiment 1, the difference is that being that reaction kettle is added in 1.2mol/L potassium silicate aqueous solution by 50ml concentration
It is interior, stirring is opened, is warming up to 50 DEG C.1.1mol/L potassium silicate aqueous solution and 1.25mol/L is added with 4ml/min flow velocity cocurrent
Aqueous sulfuric acid, while ethanol water (ethyl alcohol and the water volume that mass fraction is 6% potassium carbonate are added with 5ml/min cocurrent
Than for 1:6).Other conditions are same as Example 1.Test result is as shown in table 1.
Embodiment 3
Preparation process with embodiment 1, unlike with 4ml/min flow velocity cocurrent be added 1.1mol/L sodium silicate aqueous solution with
The aqueous solution of nitric acid of 1.3mol/L, while the ethanol water (second that mass fraction is 6% sodium carbonate is added with 5ml/min cocurrent
Alcohol and water volume ratio be 1:5) and zinc nitrate and aluminum nitrate mixed aqueous solution (two kind nitrate molar ratios of the mass fraction for 4%
When solution ph reaches 11 in reaction kettle stop that above-mentioned mixed solution, isothermal reaction 2.0h is added for 1:1.2) 25ml.With
The nitric acid n-butanol aqueous solution (n-butanol and water volume ratio are 1:10) that concentration is 1.0mol/L, solution is added in 6ml/min flow velocity
Stop that nitric acid butanol solution, isothermal reaction 2.0h is added when pH value is 9.Reaction system is warming up to 85 DEG C, isothermal reaction
5.0h.Addition concentration is 1.0mol/L aqueous solution of nitric acid, stops being added when solution ph is 4.Other conditions and 1 phase of embodiment
Together.Test result is as shown in table 1.
Embodiment 4
Preparation process is with embodiment 1, the difference is that being that reaction kettle is added in 1.2mol/L sodium silicate solution by 50ml concentration
It is interior, stirring is opened, is warming up to 50 DEG C.1.1mol/L sodium silicate aqueous solution and 1.25mol/L is added with 4ml/min flow velocity cocurrent
Aqueous sulfuric acid, while ethanol water (ethyl alcohol and the water volume that mass fraction is 6% sodium carbonate are added with 5ml/min cocurrent
Than the magnesium nitrate for being 4% for 1:9) and mass fraction and aluminum nitrate mixed aqueous solution (two kinds of nitrate molar ratios are 1:1.7)
25ml when solution ph reaches 12 in reaction kettle stops that above-mentioned mixed solution, isothermal reaction 2.0h is added.It is flowed with 6ml/min
The sulfuric acid n-butanol aqueous solution (n-butanol and water volume ratio are 1:20) that concentration is 1.0mol/L is added in speed, when solution ph is 10
Stop that sulfuric acid butanol solution, isothermal reaction 2.0h is added.Other conditions are same as Example 1.Test result is as shown in table 1.
Embodiment 5
Preparation process is with embodiment 1, the difference is that the ethyl alcohol that mass fraction is 6% sodium carbonate is added with 5ml/min cocurrent
The magnesium nitrate and aluminum nitrate mixed aqueous solution (two kinds of nitric acid that aqueous solution (ethyl alcohol and water volume ratio are 1:6) and mass fraction are 4%
Salt molar ratio is 1:1.5) 25ml, and other conditions are same as Example 1.Test result is as shown in table 1.
Embodiment 6
Preparation process is with embodiment 1, the difference is that sulfuric acid 1 of the concentration for 1.0mol/L, 3- fourth is added with 6ml/min flow velocity
Two alcohol solutions (1,3-BDO is 1:15 with water volume ratio), stop that sulfuric acid 1,3-BDO water is added when solution ph is 9
Solution, isothermal reaction 2.0h.Other conditions are same as Example 1.Test result is as shown in table 1.
Embodiment 7
Preparation process is with embodiment 1, the difference is that reaction system is warming up to 90 DEG C, isothermal reaction 5h.Concentration, which is added, is
1.0mol/L aqueous sulfuric acid stops being added when solution ph 3.Other conditions are same as Example 1.Test result such as table 1
It is shown.
Comparative example 1
It is that 1.2mol/L sodium silicate solution is added in reaction kettle by 50ml concentration, opens stirring, be warming up to 50 DEG C.With
The aqueous sulfuric acid of 1.1mol/L sodium silicate aqueous solution and 1.25mol/L is added in 4ml/min flow velocity cocurrent, when solution in reaction kettle
When pH value reaches 11, stop that above two mixed solution, isothermal reaction 2.0h is added.Concentration, which is added, with 6ml/min flow velocity is
The aqueous sulfuric acid of 1.0mol/L stops that sulfuric acid solution, isothermal reaction 2.0h is added when solution ph is 9.By reaction system liter
Temperature is to 85 DEG C, isothermal reaction 5.0h.Addition concentration is 1.0mol/L aqueous sulfuric acid, stops being added when solution ph is 4.It is cold
But respectively three times through the washing of distilled water, distilled water and alcohol mixeding liquid, then dry at 335 DEG C to room temperature, later in inertia
Under gas shield, is activated 4 hours at 600 DEG C and obtain carrier silica gel product.Test result is as shown in table 1.
Comparative example 2
It is that 1.2mol/L sodium silicate solution is added in reaction kettle by 50ml concentration, opens stirring, be to slowly warm up to 50 DEG C.
The aqueous sulfuric acid of 1.1mol/L sodium silicate aqueous solution and 1.25mol/L is added, while with 4ml/min flow velocity cocurrent with 5ml/
Min cocurrent be added mass fraction be the aqueous solution of 6% sodium carbonate and magnesium nitrate that mass fraction is 4% mixed with aluminum nitrate it is water-soluble
It is molten to stop the above-mentioned mixing of addition when solution ph reaches 11 in reaction kettle by liquid (two kinds of nitrate molar ratios are 1:2.5) 25ml
Liquid, isothermal reaction 2.0h.Concentration is added as sulfuric acid n-butanol aqueous solution (n-butanol and the water of 1.0mol/L with 6ml/min flow velocity
Volume ratio is 1:15), stop that sulfuric acid butanol solution, isothermal reaction 2.0h is added when solution ph is 9.Reaction system is heated up
To 85 DEG C, isothermal reaction 5.0h.Addition concentration is 1.0mol/L aqueous sulfuric acid, stops being added when solution ph is 4.It is cooling
It is respectively three times through the washing of distilled water, distilled water and alcohol mixeding liquid, then dry at 335 DEG C to room temperature, later in indifferent gas
Under body protection, is activated 4 hours at 600 DEG C and obtain carrier silica gel product.Test result is as shown in table 1.
Comparative example 3
It is that 1.2mol/L sodium silicate solution is added in reaction kettle by 50ml concentration, opens stirring, be to slowly warm up to 50 DEG C.
The aqueous sulfuric acid of 1.1mol/L sodium silicate aqueous solution and 1.25mol/L is added, while with 4ml/min flow velocity cocurrent with 5ml/
Min cocurrent addition mass fraction is the ethanol water (ethyl alcohol is 1:6 with water volume ratio) of 6% sodium carbonate and mass fraction is
4% magnesium nitrate and aluminum nitrate mixed aqueous solution (two kinds of nitrate molar ratios are 1:0.5) 25ml, when solution ph in reaction kettle
When reaching 11, stop that above-mentioned mixed solution, isothermal reaction 2.0h is added.It is 1.0mol/L's that concentration, which is added, with 6ml/min flow velocity
Aqueous sulfuric acid stops that sulfuric acid solution, isothermal reaction 2.0h is added when solution ph is 9.Reaction system is warming up to 85 DEG C, perseverance
Temperature reaction 5.0h.Addition concentration is 1.0mol/L aqueous sulfuric acid, stops being added when solution ph is 4.It is cooled to room temperature, point
Not three times through the washing of distilled water, distilled water and alcohol mixeding liquid, then dry at 335 DEG C, later under inert gas protection,
It is activated 4 hours at 600 DEG C and obtains carrier silica gel product.Test result is as shown in table 1.
Comparative example 4
It is that 1.2mol/L sodium silicate solution is added in reaction kettle by 50ml concentration, opens stirring, be to slowly warm up to 50 DEG C.
The aqueous sulfuric acid of 1.1mol/L sodium silicate aqueous solution and 1.25mol/L is added, while with 4ml/min flow velocity cocurrent with 5ml/
Min cocurrent be added mass fraction be the aqueous solution of 6% sodium carbonate and magnesium nitrate that mass fraction is 4% mixed with aluminum nitrate it is water-soluble
It is molten to stop the above-mentioned mixing of addition when solution ph reaches 11 in reaction kettle by liquid (two kinds of nitrate molar ratios are 1:1) 25ml
Liquid, isothermal reaction 2.0h.Concentration is added as the aqueous sulfuric acid of 1.0mol/L with 6ml/min flow velocity, solution ph stops when being 9
Aqueous sulfuric acid, isothermal reaction 2.0h is added.Reaction system is warming up to 85 DEG C, isothermal reaction 5.0h.Concentration, which is added, is
1.0mol/L aqueous sulfuric acid stops being added when solution ph is 4.It is cooled to room temperature, respectively through distilled water, distilled water and second
Alcohol mixed liquor washs three times, then dry at 335 DEG C, later under inert gas protection, activates 4 hours and obtains at 600 DEG C
Carrier silica gel product.Test result is as shown in table 1.
1 carrier silica gel physical property measurement result of table
| Project | Specific surface area/(m2/g) | Kong Rong/(cm3/g) | Aperture/nm |
| Embodiment 1 | 533.1 | 2.28 | 17.11 |
| Embodiment 2 | 527.6 | 2.23 | 16.91 |
| Embodiment 3 | 530.3 | 2.19 | 16.52 |
| Embodiment 4 | 524.5 | 2.21 | 16.85 |
| Embodiment 5 | 526.2 | 2.23 | 16.95 |
| Embodiment 6 | 525.3 | 2.22 | 16.90 |
| Embodiment 7 | 526.3 | 2.24 | 17.02 |
| Comparative example 1 | 276.4 | 1.38 | 19.97 |
| Comparative example 2 | 388.4 | 1.79 | 18.43 |
| Comparative example 3 | 401.8 | 1.72 | 17.12 |
| Comparative example 4 | 378.2 | 1.62 | 17.13 |
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (7)
1. a kind of preparation method of olefin catalytic carrier silica gel, which is characterized in that using silicate, inorganic acid as raw material, preparation
Process is as follows:
1) using aqueous silicate solution as bottom liquid；
2) aqueous silicate solution and inorganic acid aqueous solution is added in cocurrent, while the ethanol water of alkali carbonate is added in cocurrent
With the mixed aqueous solution of two kinds of nitric acid metal salts；
3) adjustment reacting solution pH value is 10~12；
4) volume ratio of the organic alcohol solution of addition inorganic acid, Organic Alcohol and water is 1:5~1:30, adjusts reacting solution pH value
It is 9~10；
5) in 70~100 DEG C of hydro-thermal reactions；
6) silica gel product is obtained after acidified, washing, dry, activation.
2. the preparation method of carrier silica gel according to claim 1, which is characterized in that the preparation process is as follows:
1) it is that 1.0~3.0mol/L aqueous silicate solution is added in reaction kettle by 30ml~60ml concentration, heats up under stirring condition
To 40 DEG C~60 DEG C；
2) 1.0~3.0mol/L aqueous silicate solution is added in cocurrent and 1.0~3.0mol/L inorganic acid aqueous solution, flow control exist
3~6ml/min, while the ethanol water and quality point for the alkali carbonate that mass fraction is 3%~10% is added in cocurrent
10~the 30ml of mixed aqueous solution for two kinds of nitric acid metal salts that number is 2%~8%, flow control is in 4~7ml/min；Alkali metal
In the ethanol water of carbonate, the volume ratio of ethyl alcohol and water is 1:1~1:10, preferably 1:5~1:9；
3) when reacting solution pH value reaches 10~12, stop that above-mentioned mixed solution, 1.0~2.5h of isothermal reaction is added；
4) organic alcohol solution for the inorganic acid that concentration is 1.0~3.0mol/L is added, flow control is organic in 4~9ml/min
The volume ratio of alcohol and water is 1:5~1:30, preferably 1:10~1:20, and adjustment solution ph is 9~10, isothermal reaction 1.0~
2.5h；
5) 3.0~5.0h of hydro-thermal reaction under the conditions of 70~100 DEG C；
6) inorganic acid aqueous solution of 1.0~3.0mol/L is added after reaction, adjustment solution ph is 3~6, reaction system drop
To room temperature, washed using distilled water or distilled water and alcohol mixeding liquid, it is then dry at 300~335 DEG C, then in inert gas
3.0h~6.0h is activated when condition, 400~600 DEG C of temperature, and carrier silica gel is made.
3. the preparation method of carrier silica gel according to claim 1 or 2, which is characterized in that the silicate is selected from silicic acid
One or more of sodium, potassium silicate, waterglass, preferably waterglass, the concentration of the aqueous silicate solution is 1.0~
1.5mol/L。
4. the preparation method of carrier silica gel according to claim 1 or 2, which is characterized in that the inorganic acid be selected from sulfuric acid,
One or more of hydrochloric acid, nitric acid, preferably sulfuric acid, the concentration of the inorganic acid aqueous solution are 1.0~1.3mol/L.
5. the preparation method of carrier silica gel according to claim 1 or 2, which is characterized in that the alkali carbonate choosing
From one or more of potassium carbonate, sodium carbonate, mass fraction is 4%~7%.
6. the preparation method of carrier silica gel according to claim 1 or 2, which is characterized in that described two nitric acid metal salts
Two kinds in magnesium nitrate, aluminum nitrate, nickel nitrate, manganese nitrate, cobalt nitrate, chromic nitrate, terbium nitrate, cerous nitrate, preferably nitric acid
The mixing of magnesium and aluminum nitrate or the mixing of zinc nitrate and aluminum nitrate, the molar ratio of two of them nitrate are 1:1~1:2, preferably
1:1~1:1.5.
7. the preparation method of carrier silica gel according to claim 1 or 2, which is characterized in that the Organic Alcohol is selected from positive fourth
Alcohol, isobutanol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 1- amylalcohol, 2- amylalcohol, 3- amylalcohol, 2-methyl-1-butene
Alcohol, 2- methyl -2- butanol, 3- methyl -2- butanol, 3- methyl-1-butanol, at least one of 2,2- dimethyl -1- propyl alcohol are excellent
Select n-butanol, 1,3 butylene glycol.
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| CN111234057A (en) * | 2020-03-25 | 2020-06-05 | 上海弘岸化工有限公司 | Silica gel carrier, silica gel-loaded alkylaluminium metallocene catalyst, long-chain branched polyethylene, and preparation method and application thereof |
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