CN114057912B - Drying method and preparation method for controlling particle morphology of chromium-loaded silica gel - Google Patents
Drying method and preparation method for controlling particle morphology of chromium-loaded silica gel Download PDFInfo
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- C08F4/00—Polymerisation catalysts
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
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Abstract
A drying method and a preparation method for controlling particle morphology of chromium-loaded silica gel belong to the technical field of drying of chromium-loaded silica gel. The invention discovers the influence of the particle morphology of the chromium-carrying silica gel on the catalytic effect of the chromium-carrying silica gel, and the inventor uses the dryness degree as an index for controlling the stirring intervention or not, effectively maintains the original particle morphology of silica gel particles, and uses acetone as an evaporation part instead of acetone before drying to improve the effect and activity of the catalyst. When the drying process is started, the volume of the part to be evaporated contained in the mixed system of the chromium salt compound and the silica gel is recorded as V, and the volume of the part to be evaporated discharged in the drying process is recorded as V 1 The dryness of the chromium-loaded silica gel was noted as g=v 1 V×100%, stopping stirring when the dryness G reaches or exceeds 65% and is less than 75%; the drying degree G reaches or exceeds 80 percent and reaches or is less than 90 percent at any time, and stirring is started, so that the chromium-carrying silica gel has the optimal catalytic state.
Description
Technical Field
A drying method and a preparation method for controlling particle morphology of chromium-loaded silica gel belong to the technical field of drying of chromium-loaded silica gel.
Background
Chromium-loaded silica gels are an important class of catalysts in the polyolefin industry. The preparation method is that chromium source is loaded on catalyst carrier such as silica gel or silica gel-alumina, and then the loaded catalyst is obtained through thermal activation or chemical activation. The supported chromium catalyst has been widely used in polyethylene production processes by solution, slurry and gas phase processes.
The chromium-loaded silica gel catalyst is generally participated in the reaction in the form of particles, the form of the particles often plays an extremely important role, the particles are broken, the supported catalytic efficiency is reduced, the particles are too small, the surface area is too large, the catalytic process is extremely short, and the polymer can possibly undergo uncontrollable reactions such as bursting polymerization; particle aggregation, the catalytic efficiency is low; the non-uniformity of the particles easily results in non-uniform catalytic efficiency, resulting in a large amount of catalyst waste.
In the prior art, many researchers pay attention to the research of high-temperature thermal activation of a silica gel carrier, the catalytic efficiency is controlled by improving the activation degree of a catalyst finished product, and the influence of the particle morphology on the catalytic effect is ignored.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the drying method and the preparation method for controlling the particle morphology of the chromium-loaded silica gel are provided, and the morphology of the final particles can be effectively maintained.
The technical scheme adopted for solving the technical problems is as follows: a drying method and a preparation method for controlling particle morphology of chromium-loaded silica gel are characterized in that: and controlling the morphology of particles by using the different drying degrees of the chromium-loaded silica gel in the drying process and starting or closing the stirring intervention.
The inventors of the present application have found that the original particle morphology of silica gel particles can be effectively maintained by using the relationship between the degree of dryness and stirring, using the degree of dryness as an index for controlling the intervention of stirring.
Preferably, in the drying process, the volume of the evaporation part to be used in the mixed dispersion system of the chromium salt compound and the silica gel is denoted as V at the beginning, and the volume of the evaporation part discharged in the drying process is denoted as V 1 The dryness of the chromium-loaded silica gel is marked as G;
G= V 1 ÷V×100%；
in the drying process, the stirring intervention is stopped at any moment when the drying degree G reaches or is more than 65% and less than 75%; and continuing to dry until the drying degree G reaches or exceeds 80 percent and reaches or is less than 90 percent at any time, starting stirring intervention, and drying until the required particle state is achieved.
Preferably, when the dryness G reaches 70%, stopping stirring intervention; and (5) continuing to dry until the drying degree G reaches 82%, starting stirring intervention, and drying to the required particle state to finish drying.
In the drying of powder materials, it is generally known that powder particles are subjected to continuous stirring, and continuous stirring is beneficial to the drying process, and this is beneficial to less regular particles, and particle aggregation can be avoided, but this method is easy to ignore the influence on the strength of powder particles, and is a detrimental factor to silica gel carriers with higher regularity. Therefore, the drying process of the carrier particles is effectively controlled, and proper control indexes are found to effectively solve the problems, so that the generation of particle aggregation state can be avoided, the particle strength can be maintained, and the particle breakage is reduced, which is a key point of the invention.
The preparation method of the chromium-loaded silica gel comprises the following steps:
1) And adding 1-2.5 parts by weight of chromium salt compound into distilled water at 40-60 ℃ under stirring, and stirring until the chromium salt compound is fully dissolved into a chromium salt compound aqueous solution.
2) And adding distilled water at 40-60 ℃ and 250-400 parts by weight of silica gel into a reaction kettle with a gas-liquid separator at the upper part, and uniformly stirring.
3) Adding the aqueous solution in the step 1) into the reaction kettle in the step 2), uniformly stirring, and recording that the total volume of distilled water used in the step 1) and the step 2) is V 2 。
4) Stopping stirring, standing to obtain supernatant, and collecting the supernatant volume denoted by V 3 Each time with V 2 -V 3 Washing 3 times or more with acetone; the part to be evaporated in the system can be considered to have been replaced by acetone at this time.
5) The reaction kettle is set at 100-120 ℃ and is filled with nitrogen to start the drying process, the nitrogen carries acetone vapor to enter a gas-liquid separator, and the volume of acetone after the acetone vapor is collected and condensed is recorded as V 1 。
6) When the drying process starts, the part to be evaporated, namely the residual acetone volume, contained in the mixed system of the chromium salt compound and the silica gel is recorded as V, and then: v=v 2 - V 3 ；
Continuously calculating the drying degree G to a required particle state in the drying process, and recording the drying degree G of the chromium-loaded silica gel;
G= V 1 ÷V×100%。
in the drying process, the stirring intervention is stopped at any moment when the drying degree G reaches or is more than 65% and less than 75%; and continuing to dry until the drying degree G reaches or exceeds 80 percent and reaches or is less than 90 percent at any time, starting stirring intervention, and drying until the required particle state is achieved.
The acetone is used for washing to replace water to become volatile matters, so that on one hand, the temperature required by drying can be effectively reduced, energy is saved, and on the other hand, the acetone can better disperse silica gel particles, so that the final chromium-carrying silica gel particles are kept more complete, and the activity of the catalyst can be improved.
Preferably, 0.25-2 parts by weight of dodecyl dimethyl benzyl ammonium chloride is added into the distilled water in the step 1). The addition of dodecyl dimethyl benzyl ammonium chloride can improve the impregnation effect of the two solutes in the following step 1) and step 2), shorten the impregnation time, effectively avoid the influence of long-time impregnation or insufficient impregnation on chromium-carrying silica gel particles, improve the strength of the final catalyst and avoid crushing.
Preferably, the chromium salt compound in the step 1) is one or a mixture of a plurality of acetate, dichromate, chromate, nitrate of chromium or oxide of chromium in any proportion.
Preferably, the chromium salt compound in step 1) is chromium acetate. Acetate dissolution rate is faster and toxicity is smaller.
Preferably, the specific surface area of the silica gel in the step 2) is 150-500 m 2 Per gram, the pore volume is 1.5-3 mL/g, and the diameter of the pore diameter particles is 30-120 mu m.
Compared with the prior art, the invention has the following beneficial effects: the drying degree is used as an index for controlling stirring intervention or not, the original particle form of silica gel particles can be effectively maintained by using the relation between the drying degree and stirring intervention, and the specific relation between the drying degree and stirring intervention is determined, so that the original particle form of the silica gel particles can be maintained to the greatest extent after the silica gel particles are dried, the final catalyst has small particle size distribution, uniform particles and no aggregation and is excessively broken, and the catalytic effect of the final chromium-loaded silica gel is effectively improved.
Detailed Description
Examples 5 and 6 are preferred embodiments of the present invention, and the present invention will be further described with reference to examples.
Example 1
A drying method and a preparation method for controlling particle morphology of chromium-loaded silica gel comprise the following steps:
(1) Aqueous solutions of chromium salt compounds. Under stirring, 1L of distilled water is heated to 50 ℃, 2.4g of chromium acetate is added, and the temperature is kept to be fully dissolved, so that the chromium salt compound aqueous solution can be obtained.
(2) And (3) dispersing silica gel. A10L reactor was prepared, the upper part of which was provided with a gas-liquid separator, 600g of silica gel and 5L of distilled water were added into the reactor, and stirred for 0.5 hour at a stirring speed of 150 rpm, and the temperature of the reactor was controlled at 50 ℃.
(3) Dipping. Slowly adding the chromium salt compound solution obtained in the step (1) into a reaction kettle, stirring for 2 hours at a stirring speed of 150 rpm, and controlling the temperature of the reaction kettle at 50 ℃. The volume of distilled water used in step (1) and step (2) is V 2 。
(4) And (5) settling and separating. Stopping stirring in the reaction kettle, allowing silica gel particles to naturally settle for 3 hours, then extracting supernatant, and recording volume of the extracted supernatant as V 3 Each time with V 2 -V 3 Washing 3 times with acetone volume, total using 3 times the volume of acetone V 2 -V 3 At this point, the part to be evaporated in the system can be considered to have been replaced with acetone.
(5) And (5) drying. Stirring is started, the stirring rotation speed is 50 r/min, nitrogen is introduced into the upper part of the reaction kettle, the flow rate of the nitrogen is 5 l/min, the temperature of the reaction kettle is controlled to be 110 ℃, drying is started, acetone steam enters the gas-liquid separator under the driving of stirring and nitrogen, the nitrogen is discharged through the gas outlet of the gas-liquid separator, the acetone steam is condensed in the gas-liquid separator and then enters the liquid collecting bottle, and the volume of the condensed acetone is recorded as V 1 。
(6) When the drying process starts, the volume of the to-be-evaporated part, namely the acetone, contained in the mixed system of the chromium salt compound and the silica gel is recorded as V, and then: v=v 2 - V 3 ；
When the degree of dryness g=v 1 When the ratio of V.times.100% reaches 60%, stirring is stopped, and when the drying degree G reaches 90%, stirring is started at a rotation speed of 50 rpm.
(7) And (5) analyzing the discharge. And sampling the silica gel in the reaction kettle in the drying process, and discharging after the drying is finished when the volatile matters of the silica gel are less than 0.8%.
The results of the particle size analysis are shown in Table 1 below.
Example 2
In comparison with example 1, the drying method and the preparation method for controlling the particle morphology of the chromium-loaded silica gel set the switch stirring condition in the step (6) as follows:
when the degree of dryness g=v 1 ÷V×100%, when 67% is reached, stirring is stopped, and when the dryness G reaches 82%, stirring is started, and the rotation speed is 50 rpm.
The other steps were the same, and the results of the particle size analysis are shown in Table 1 below.
Example 3
In comparison with example 1, the drying method and the preparation method for controlling the particle morphology of the chromium-loaded silica gel set the switch stirring condition in the step (6) as follows:
when the degree of dryness g=v 1 When 65% of the mixture is reached, stirring is stopped, and when 87% of the mixture is reached, stirring is started at a rotation speed of 50 rpm.
The other steps were the same, and the results of the particle size analysis are shown in Table 1 below.
Example 4
In comparison with example 1, the drying method and the preparation method for controlling the particle morphology of the chromium-loaded silica gel set the switch stirring condition in the step (6) as follows:
when the degree of dryness g=v 1 When the ratio of V.times.100% reaches 60%, stirring is stopped, and when the drying degree G reaches 80%, stirring is started at a rotation speed of 50 rpm.
The other steps were the same, and the results of the particle size analysis are shown in Table 1 below.
Example 5
In comparison with example 1, the drying method and the preparation method for controlling the particle morphology of the chromium-loaded silica gel set the switch stirring condition in the step (6) as follows:
when the degree of dryness g=v 1 When the ratio of V.times.100% reaches 70%, stirring is stopped, and when the dryness G reaches 82%, stirring is started at a rotation speed of 50 rpm.
The other steps were the same, and the results of the particle size analysis are shown in Table 1 below.
Example 6
A method for drying and preparing chromium-loaded silica gel to control particle morphology, compared with example 1, wherein 1.5g of dodecyl dimethyl benzyl ammonium chloride is added before adding chromium salt compound in step (1), and the other steps are the same.
The results of the particle size analysis are shown in Table 1 below.
Comparative example 1
Compared with the method for drying the chromium-loaded silica gel to control the particle morphology and the preparation method, the method for drying the chromium-loaded silica gel has the advantages that compared with the method for drying the chromium-loaded silica gel in the example 1, the operation process of the step (6) is not arranged, and when the chromium-loaded silica gel is directly dried to the volatile content of less than 0.8% under the stirring state, the drying is finished, and the discharging is carried out.
The other steps were the same, and the results of the particle size analysis are shown in Table 1 below.
Comparative example 2
In comparison with example 1, the drying method and the preparation method for controlling the particle morphology of the chromium-loaded silica gel set the switch stirring condition in the step (6) as follows:
when the degree of dryness g=v 1 When the ratio of V.times.100% reaches 80%, stirring is stopped, and when the dryness G reaches 90%, stirring is started at a rotation speed of 50 rpm.
The other steps were the same, and the results of the particle size analysis are shown in Table 1 below.
Comparative example 3
In comparison with example 1, the drying method and the preparation method for controlling the particle morphology of the chromium-loaded silica gel set the switch stirring condition in the step (6) as follows:
when the degree of dryness g=v 1 When the ratio of V.times.100% reaches 60%, stirring is stopped, and when the drying degree G reaches 75%, stirring is started at a rotation speed of 50 rpm.
The other steps were the same, and the results of the particle size analysis are shown in Table 1 below.
Comparative example 4
Compared with the drying method and the preparation method for controlling the particle morphology of the chromium-loaded silica gel, in the embodiment 1, the clear liquid is extracted in the step 4) and then the clear liquid volume is recorded as V 2 No acetone wash was performed.
Step 5) drying. Stirring is started, the stirring speed is 50 r/min, nitrogen is introduced into the upper part of the reaction kettle, the flow rate of the nitrogen is 5 l/min, the temperature of the reaction kettle is controlled to be 110 ℃, drying is started, water vapor enters the gas-liquid separator under the driving of stirring and nitrogen, the nitrogen is discharged through a gas outlet of the gas-liquid separator, the water vapor is condensed in the gas-liquid separator and then enters a liquid collecting bottle, and the volume of the condensed water is recorded as V 1 。
Step 6) the drying process is startedAt first, the volume of distilled water which is the part to be evaporated contained in the mixed system of the chromium salt compound and the silica gel is recorded as V: v=v 2 - V 3 The method comprises the steps of carrying out a first treatment on the surface of the When the degree of dryness g=v 1 When the ratio of V.times.100% reaches 60%, stirring is stopped, and when the drying degree G reaches 90%, stirring is started at a rotation speed of 50 rpm.
The other steps were the same, and the performance test results are shown in Table 1 below.
Performance testing
Measurement of average particle size of silica gel particles the size and distribution of the particle size of silica gel was measured by a malvern Mastersizer2000 laser particle sizer wet method. Distilled water is selected as a dispersion medium, corresponding sample parameters such as refractive index, absorptivity and the like are set, and volume average particle size and particle size distribution data of the sample parameters are obtained under the appropriate experimental conditions such as pump speed, shading degree and the like.
Table 1 below shows the results of the particle size analysis, among them,
d (0.1) represents a diameter corresponding to 10% of the cumulative particle diameter distribution (0 to 100%). For example, 11.1 means that 10% of the particles have a particle size distribution of 11.1 μm or less.
d (0.5) represents a diameter corresponding to 50% of the cumulative particle diameter distribution (0 to 100%). Also called median particle diameter, for example 42.1 means that 50% of the particles have a particle size distribution below 42.1. Mu.m.
d (0.9) represents a diameter corresponding to 90% of the cumulative distribution (0 to 100%) of particle diameters. For example 86.5 means that 90% of the particles have a particle size distribution of 86.5 μm or less.
The raw materials described in the table are the state before drying of the silica gel particles used.
TABLE 1 results of particle size analysis
From the test results in table 1, it is apparent that the stirring can be turned on or off at a proper time to keep the dried carrier particles in a state closest to the raw material, and that the use of acetone instead of volatile water can effectively promote the dispersion effect of the carrier in the liquid, so as to prevent the problems of agglomeration of the particles or excessive crushing during stirring and uneven particle size distribution.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (6)
1. A preparation method of chromium-loaded silica gel is characterized in that: the method comprises the following steps:
1) Adding 1-2.5 parts by weight of chromium salt compound into distilled water at 40-60 ℃ under stirring, and stirring until the chromium salt compound is fully dissolved into a chromium salt compound aqueous solution;
2) Adding distilled water at 40-60 ℃ and 250-400 parts by weight of silica gel into a reaction kettle with a gas-liquid separator at the upper part, and uniformly stirring;
3) Adding the aqueous solution in the step 1) into the reaction kettle in the step 2), uniformly stirring, and recording that the total volume of distilled water used in the step 1) and the step 2) is V 2 ；
4) Stopping stirring, standing to obtain supernatant, and collecting the supernatant volume denoted by V 3 Each time with V 2 -V 3 Washing 3 times or more with acetone;
5) The reaction kettle is set at 100-120 ℃ and is filled with nitrogen to start the drying process, the nitrogen carries acetone vapor to enter a gas-liquid separator, and the volume of acetone after the acetone vapor is collected and condensed is recorded as V 1 ；
6) When the drying process starts, the volume of the part to be evaporated contained in the mixed system of the chromium salt compound and the silica gel is recorded as V, and then: v=v 2 - V 3 The method comprises the steps of carrying out a first treatment on the surface of the Continuously calculating the drying degree G to a required particle state in the drying process, and recording the drying degree G of the chromium-loaded silica gel; g=v 1 V×100%; controlling particles by using different drying degrees of the chromium-loaded silica gel in the drying process and starting or closing the stirring interventionForm of (2);
in the drying process, the stirring intervention is stopped at any moment when the drying degree G reaches or is more than 65% and less than 75%; and continuing to dry until the drying degree G reaches or exceeds 80 percent and reaches or is less than 90 percent at any time, starting stirring intervention, and drying until the required particle state is achieved.
2. The method for preparing the chromium-loaded silica gel according to claim 1, wherein: stopping stirring intervention when the dryness G reaches 70%; and (5) continuing to dry until the drying degree G reaches 82%, starting stirring intervention, and drying to the required particle state to finish drying.
3. The method for preparing the chromium-loaded silica gel according to claim 1, wherein: and 1) adding 0.25-2 parts by weight of dodecyl dimethyl benzyl ammonium chloride into the distilled water in the step 1).
4. The method for preparing the chromium-loaded silica gel according to claim 1, wherein: the chromium salt compound is one or a mixture of a plurality of acetate, dichromate, chromate, nitrate of chromium or oxide of chromium in any proportion.
5. The method for preparing chromium-carrying silica gel according to claim 4, wherein: the chromium salt compound is acetate of chromium.
6. The method for preparing the chromium-loaded silica gel according to claim 1, wherein: the specific surface area of the silica gel in the step 2) is 150-500 m 2 Per gram, the pore volume is 1.5-3 mL/g, and the diameter of the pore diameter particles is 30-120 mu m.
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