CN113461883A - Preparation method of phenolic resin microspheres - Google Patents
Preparation method of phenolic resin microspheres Download PDFInfo
- Publication number
- CN113461883A CN113461883A CN202110864333.9A CN202110864333A CN113461883A CN 113461883 A CN113461883 A CN 113461883A CN 202110864333 A CN202110864333 A CN 202110864333A CN 113461883 A CN113461883 A CN 113461883A
- Authority
- CN
- China
- Prior art keywords
- phenolic resin
- stirring
- mixed solution
- resin microspheres
- alkaline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 138
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 138
- 239000004005 microsphere Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 103
- 239000011259 mixed solution Substances 0.000 claims abstract description 77
- 238000001723 curing Methods 0.000 claims abstract description 68
- 238000002156 mixing Methods 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000011159 matrix material Substances 0.000 claims abstract description 34
- -1 phenolic aldehyde Chemical class 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000006482 condensation reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 17
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 21
- 239000002994 raw material Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
Abstract
The invention relates to the technical field of preparation of spherical activated carbon, in particular to a method for preparing phenolic resin microspheres. In order to realize the large-scale production of the phenolic resin microspheres and reduce the production cost, the invention provides a preparation method of the phenolic resin microspheres, which comprises the steps of placing phenol, formaldehyde, an alkaline curing agent, a surfactant and solvent water into a reactor, stirring and mixing to obtain a phenolic homogeneous phase solution; adding an alkaline catalyst into the phenolic aldehyde homogeneous phase solution to obtain an alkaline mixed solution, adjusting the reaction temperature of the mixed solution to 70-95 ℃, and stirring for condensation reaction to form phenolic resin oil drops; raising the reaction temperature of the mixed solution to the reflux temperature, and continuously stirring to pre-cure phenolic resin oil drops to form a phenolic resin microsphere matrix; and taking out the phenolic resin microsphere matrix, washing, filtering, and curing in a drying oven to obtain the phenolic resin microspheres. The preparation method of the phenolic resin microspheres can reduce the preparation cost, is beneficial to volume production and realizes the large-scale production of the phenolic resin microspheres.
Description
Technical Field
The invention relates to the technical field of preparation of spherical activated carbon, in particular to a method for preparing phenolic resin microspheres.
Background
Most of the commercially available activated carbons use coal or biological materials as carbon sources, but the activated carbons have irregular structures, also have the defects of wide gap distribution range, high ash content and the like, and are complicated to treat after use. The microspherical activated carbon has the advantages of controllable shape, good rolling property, high mechanical strength, large specific surface area, strong adsorption capacity and the like, so the microspherical activated carbon has great application potential in the fields of catalyst carriers, toxic gas adsorption, hemodialysis and the like.
At present, phenolic resin is usually used as a raw material, a suspension method is adopted to prepare phenolic resin microspheres, and the phenolic resin microspheres are carbonized and activated to form microspherical activated carbon. In the prior art, there are various methods for preparing phenolic resin microspheres, for example, in the preparation methods disclosed in patent documents CN98118911.3 and CN98115717.3, the phenolic resin novolac and the curing agent are mixed and then crushed, dispersed and cured at high temperature to form resin microspheres, which is complicated in process and high in cost; although the preparation method disclosed in patent document No. cn200410012346.x simplifies the pulverization process, a large amount of ethanol and a high-temperature curing environment are still required, so that the sphere diameter of the prepared resin microspheres is difficult to control; the processes for preparing the phenolic resin microspheres disclosed in patent documents CN200910200119.2 and CN201110329424.9 need high rotating speed and ultrahigh temperature curing, and large-scale production is difficult to realize. In conclusion, the existing method for preparing the phenolic resin microspheres is complicated in process and high in cost, or needs high-temperature curing and is difficult to produce in a large scale.
Disclosure of Invention
In order to realize the large-scale production of the phenolic resin microspheres and reduce the production cost, the invention provides a preparation method of the phenolic resin microspheres, which comprises the following steps:
step S1: placing phenol, formaldehyde, an alkaline curing agent, a surfactant and solvent water into a reactor, stirring and mixing to obtain a phenolic homogeneous phase solution;
step S2: adding an alkaline catalyst into the phenolic aldehyde homogeneous phase solution to obtain an alkaline mixed solution, adjusting the reaction temperature of the mixed solution to 70-95 ℃, and stirring the mixed solution for condensation reaction to form phenolic resin oil drops;
step S3: raising the reaction temperature of the mixed solution to the reflux temperature, and continuously stirring the mixed solution to pre-cure the phenolic resin oil drops to form a phenolic resin microsphere matrix;
step S4: and taking the phenolic resin microsphere matrix out of the reactor, washing, filtering, and curing in a drying oven to obtain the phenolic resin microspheres.
According to the preparation method of the phenolic resin microspheres, the surfactant is adopted to uniformly blend the phenol, the formaldehyde and the alkaline curing agent in the solvent water to form a weakly alkaline environment, so that the reaction rate, namely the rate of forming phenolic resin oil drops, can be controlled by controlling the stirring speed and the reaction temperature of the mixed solution, the phenolic resin oil drops can be ensured to be uniformly formed, the crushing process during the preparation of the phenolic resin microspheres is avoided, and the preparation cost of the phenolic resin microspheres is reduced; the water is used as the solvent, so that a large amount of ethanol can be saved, the reflux temperature of the mixed solution can be controlled to be about 100 ℃, and the cost for preparing the phenolic resin is effectively reduced; the phenolic resin microsphere matrix formed by precuring phenolic resin oil drops is dried and cured by adopting the drying oven to obtain the phenolic resin microspheres, so that the prepared phenolic resin microspheres have high and controllable shape yield, the mass production is facilitated, meanwhile, the mixed liquid can be prevented from being cured in a high-temperature and high-pressure environment, and the curing difficulty and risk are reduced. In conclusion, the preparation method of the phenolic resin microspheres can reduce the preparation cost of the phenolic resin microspheres, is favorable for large-scale production, and realizes the large-scale production of the phenolic resin microspheres.
Preferably, in step S1, the basic curing agent is urotropin. Thus, urotropine is used as an alkaline curing agent and added into solvent water, so that phenol and formaldehyde in the mixed phenolic aldehyde homogeneous phase solution can not be crosslinked to form phenolic resin oil drops under acidic conditions. Further, the weight ratio of the phenol, the formaldehyde, the alkaline curing agent, the surfactant and the solvent water is as follows: the weight portion of the phenol is 100 portions, the weight portion of the formaldehyde is 35-52 portions, the weight portion of the alkaline curing agent is 2-5 portions, the weight portion of the surfactant is 5-20 portions, and the weight portion of the solvent water is 500-900 portions. Further preferably, when the phenolic aldehyde homogeneous phase solution is obtained by stirring and mixing, the stirring and mixing speed is 150-200 r/min, the stirring and mixing time is 10-30 minutes, the stirring and mixing temperature is 60-80 ℃, and the stirring and mixing pressure is normal pressure. Thus, when the phenolic aldehyde homogeneous phase solution formed by mixing the phenol, the formaldehyde, the alkaline curing agent, the surfactant and the solvent water is stirred and mixed, the stirring and mixing speed is controlled to be 150-200 r/m, the stirring and mixing time is controlled to be 10-30 min, the stirring and mixing temperature is controlled to be 60-80 ℃, and the stirring and mixing pressure is controlled to be normal pressure, so that the stirring and mixing conditions can be effectively reduced, and the feasibility of large-scale production of the phenolic resin microspheres can be further improved.
Preferably, in step S2, the alkaline catalyst is KOH, NaOH, ammonia, or K2CO3、Na2CO3、Mg(OH)2Or Ba (OH)2And after the alkaline catalyst is added, the pH value range of the mixed solution is 8-11. Therefore, the selectable range of the alkaline catalyst is wide, and the cost for preparing the phenolic resin microspheres can be reduced; the PH value of the mixed solution is controlled to be 8-11, the content of hydroxyl ions (OH-) in the mixed solution can be controlled within a certain range, and phenoxide is prevented from being formed due to overhigh PH value of the mixed solution and being incapable of being separated out and solidified from the solvent water. Further, in the condensation reaction, the stirring speed is 300-600 r/min, the reaction time is 4-6h, the reaction pressure is normal pressure, and the temperature range is 75-90 ℃. Thus, when the condensation reaction is carried out to form the phenolic resin oil drops, the stirring speed is controlled to be 300-600 revolutions per minute, the reaction time is controlled to be 4-6 hours, the reaction pressure is controlled to be normal pressure, the temperature is controlled to be 75-90 ℃, the reaction conditions of the condensation reaction can be effectively reduced, and the scale of the phenolic resin microspheres can be further improvedFeasibility of production. Further preferably, the temperature range during the condensation reaction is 83-88 ℃. Therefore, the uniformity of phenolic resin oil drops formed in the condensation reaction process can be improved, so that the uniformity of a phenolic resin microsphere matrix formed by pre-curing can be improved, and the uniformity of phenolic resin microspheres formed by curing can be improved.
Preferably, in the step S3, when the pre-curing is performed, the stirring speed is 300-600 rpm, the reaction time is not less than 2h, and the reaction pressure is normal pressure. Therefore, when the precuring is carried out, the stirring speed is controlled to be 300-600 rpm, the reaction time is controlled to be at least 2h, and the reaction pressure is controlled to be normal pressure, so that the precuring reaction conditions can be effectively reduced, and the feasibility of large-scale production of the phenolic resin microspheres can be further improved.
Preferably, in the step S4, at least three washing filtrations are performed on the phenolic resin microsphere matrix, and the temperature of at least one washing water is higher than 60 ℃. Therefore, through multiple washing and filtering, impurities such as a surfactant, a catalyst and the like on the phenolic resin microsphere matrix are effectively removed. Furthermore, the curing temperature is T, T is more than or equal to 120 ℃ and less than or equal to 200 ℃, and the curing time T is more than or equal to 2 hours. Therefore, the curing temperature is above 100 ℃, so that the internal crosslinking of the phenolic resin microsphere matrix is more perfect in yielding water, the strength of the cured phenolic resin microspheres is stronger, and the problems that the curing time is too long and the energy is wasted due to too low curing temperature of the phenolic resin microsphere matrix can be avoided.
Drawings
FIG. 1 is an optical photograph of the phenolic resin microspheres prepared by the method of preparing phenolic resin microspheres of the present invention in example 1 after 1 hour of curing;
FIG. 2 is an optical photograph of the phenolic resin microspheres prepared by the method for preparing phenolic resin microspheres of the present invention in example 1, after being cured for 3 hours;
FIG. 3 is a comparison graph of the control effect of the stirring speed in the condensation reaction on the sphere diameter of the prepared phenolic resin microspheres when the phenolic resin microspheres are prepared by the preparation method of the phenolic resin microspheres of the present invention.
Detailed Description
The following will explain the preparation method of the phenolic resin microspheres of the present invention in detail with reference to FIGS. 1-3 and examples.
Example 1:
firstly, placing raw and auxiliary materials into a reactor for stirring and mixing to obtain a phenolic aldehyde homogeneous phase solution. The raw materials and auxiliary materials comprise the following components in parts by weight: 100 parts of phenolic aldehyde, 35 parts of formaldehyde, 5 parts of alkaline curing agent, 5 parts of surfactant and 600 parts of solvent water. When the raw and auxiliary materials are stirred and mixed, the stirring and mixing speed is 150 rpm, the stirring and mixing time is 30 minutes, the stirring and mixing temperature is 60 ℃, and the reaction pressure in the reactor is normal pressure.
And then, adding an alkaline catalyst KOH into the phenolic aldehyde homogeneous phase solution to obtain an alkaline mixed solution, adjusting the reaction temperature of the mixed solution to 80 ℃ and the pH value of the mixed solution to 11, stirring the mixed solution in a reactor at a stirring speed of 300 revolutions per minute, keeping the reaction pressure in the reactor at normal pressure, and stirring for 4 hours to perform condensation reaction on the mixed solution to form phenolic resin oil drops.
And then heating the reactor to boil the mixed solution, namely raising the reaction temperature of the mixed solution to the reflux temperature, and continuing stirring at the stirring speed of 300 revolutions per minute for 2 hours to pre-cure phenolic resin oil drops in the mixed solution to form a phenolic resin microsphere matrix.
And finally, taking the phenolic resin microsphere matrix out of the reactor, washing and filtering, placing the phenolic resin microsphere matrix in a 130 ℃ blast drying oven for curing after washing and filtering, and finishing curing after 3 hours to obtain the phenolic resin microspheres with the yield of 77.2%.
In the curing process, when the phenolic resin microspheres are cured for 1h, an optical photo of the formed phenolic resin microspheres is shown in FIG. 1; an optical photograph of the phenolic resin microspheres formed upon curing for 3h is shown in figure 2. As can be seen from fig. 1 and 2, the longer the curing time is, the darker the color of the phenolic resin microspheres formed by curing.
In addition, in the present embodiment, only the stirring speed during the pre-curing and curing processes is adjusted, and the influence of the stirring speed on the particle size of the phenolic resin microspheres formed by curing is tested, and as a result, as shown in fig. 3, when the stirring speed is 200 rpm, the sphere diameter of the phenolic resin microspheres formed by curing is concentrated at 100-; when the stirring speed is 300 r/min, the sphere diameter of the phenolic resin microspheres formed by curing is concentrated at 200-; when the stirring speed is 500 r/min, the sphere diameter of the phenolic resin microspheres formed by curing is concentrated at 300-; when the stirring speed is 600 r/min, the sphere diameter of the phenolic resin microspheres formed by curing is concentrated at 200-. Therefore, when the stirring speed is lower, the sphere diameter of the phenolic resin microspheres formed by curing is larger, and the sphere diameter interval of the phenolic resin microspheres formed is larger, namely the phenolic resin microspheres formed by curing are not uniform; when the stirring speed is higher, the sphere diameter of the phenolic resin microspheres formed by curing is smaller, and the sphere diameter interval of the phenolic resin microspheres formed is smaller, namely the phenolic resin microspheres formed by curing are more uniform.
Example 2:
firstly, placing raw and auxiliary materials into a reactor for stirring and mixing to obtain a phenolic aldehyde homogeneous phase solution. The raw materials and auxiliary materials comprise the following components in parts by weight: 100 parts of phenolic aldehyde, 40 parts of formaldehyde, 4 parts of alkaline curing agent, 10 parts of surfactant and 500 parts of solvent water. When the raw and auxiliary materials are stirred and mixed, the stirring and mixing speed is 180 r/min, the stirring and mixing time is 20 minutes, the stirring and mixing temperature is 70 ℃, and the reaction pressure in the reactor is normal pressure.
And then, adding an alkaline catalyst NaOH into the phenolic aldehyde homogeneous phase solution to obtain an alkaline mixed solution, adjusting the reaction temperature of the mixed solution to 80 ℃ and the pH value of the mixed solution to 11, stirring the mixed solution in a reactor at a stirring speed of 400 revolutions per minute, keeping the reaction pressure in the reactor at normal pressure, and stirring for 6 hours to perform condensation reaction on the mixed solution to form phenolic resin oil drops.
And then heating the reactor to boil the mixed solution, namely raising the reaction temperature of the mixed solution to the reflux temperature, and continuing stirring at the stirring speed of 400 rpm for 2 hours to pre-cure phenolic resin oil drops in the mixed solution to form a phenolic resin microsphere matrix.
And finally, taking the phenolic resin microsphere matrix out of the reactor, washing and filtering, placing the phenolic resin microsphere matrix in a 130 ℃ blast drying oven for curing after washing and filtering, and finishing curing after 3 hours to obtain the phenolic resin microspheres with the yield of 75.4%.
Example 3:
firstly, placing raw and auxiliary materials into a reactor for stirring and mixing to obtain a phenolic aldehyde homogeneous phase solution. The raw materials and auxiliary materials comprise the following components in parts by weight: 100 parts of phenolic aldehyde, 45 parts of formaldehyde, 3 parts of alkaline curing agent, 5 parts of surfactant and 900 parts of solvent water. When the raw and auxiliary materials are stirred and mixed, the stirring and mixing speed is 200 revolutions per minute, the stirring and mixing time is 10 minutes, the stirring and mixing temperature is 80 ℃, and the reaction pressure in the reactor is normal pressure.
Then, the basic catalyst K is added2CO3Adding the mixture into a phenolic aldehyde homogeneous phase solution to obtain an alkaline mixed solution, adjusting the reaction temperature of the mixed solution to 85 ℃ and the pH value of the mixed solution to 9, stirring the mixed solution in a reactor at a stirring speed of 400 rpm, keeping the reaction pressure in the reactor at normal pressure, and stirring for 4 hours to perform condensation reaction on the mixed solution to form phenolic resin oil drops.
And then heating the reactor to boil the mixed solution, namely raising the reaction temperature of the mixed solution to the reflux temperature, and continuing stirring at the stirring speed of 400 rpm for 2 hours to pre-cure phenolic resin oil drops in the mixed solution to form a phenolic resin microsphere matrix.
And finally, taking the phenolic resin microsphere matrix out of the reactor, washing and filtering, placing the phenolic resin microsphere matrix in a 130 ℃ blast drying oven for curing after washing and filtering, and finishing curing after 3 hours to obtain the phenolic resin microspheres with the yield of 70.1%.
Example 4:
firstly, placing raw and auxiliary materials into a reactor for stirring and mixing to obtain a phenolic aldehyde homogeneous phase solution. The raw materials and auxiliary materials comprise the following components in parts by weight: 100 parts of phenolic aldehyde, 35 parts of formaldehyde, 4 parts of alkaline curing agent, 20 parts of surfactant and 600 parts of solvent water. When the raw and auxiliary materials are stirred and mixed, the stirring and mixing speed is 150 rpm, the stirring and mixing time is 30 minutes, the stirring and mixing temperature is 70 ℃, and the reaction pressure in the reactor is normal pressure.
Then, the basic catalyst Na2CO3Adding the mixed solution into a phenolic aldehyde homogeneous phase solution to obtain an alkaline mixed solution, adjusting the reaction temperature of the mixed solution to 95 ℃ and the pH value of the mixed solution to 8, stirring the mixed solution in a reactor at a stirring speed of 500 revolutions per minute, keeping the reaction pressure in the reactor at normal pressure, and stirring for 5 hours to enable the mixed solution to perform condensation reaction to form phenolic resin oil drops.
And then heating the reactor to boil the mixed solution, namely raising the reaction temperature of the mixed solution to the reflux temperature, and continuing stirring at the stirring speed of 500 revolutions per minute for 4 hours to pre-cure phenolic resin oil drops in the mixed solution to form a phenolic resin microsphere matrix.
And finally, taking the phenolic resin microsphere matrix out of the reactor, washing and filtering, placing the phenolic resin microsphere matrix in a 130 ℃ blast drying oven for curing after washing and filtering, and finishing curing after 2 hours to obtain the phenolic resin microspheres with the yield of 72.8%.
Example 5:
firstly, placing raw and auxiliary materials into a reactor for stirring and mixing to obtain a phenolic aldehyde homogeneous phase solution. The raw materials and auxiliary materials comprise the following components in parts by weight: 100 parts of phenolic aldehyde, 40 parts of formaldehyde, 2 parts of alkaline curing agent, 5 parts of surfactant and 700 parts of solvent water. When the raw and auxiliary materials are stirred and mixed, the stirring and mixing speed is 170 rpm, the stirring and mixing time is 20 minutes, the stirring and mixing temperature is 80 ℃, and the reaction pressure in the reactor is normal pressure.
And then adding alkaline catalyst ammonia water into the phenolic aldehyde homogeneous phase solution to obtain alkaline mixed solution, adjusting the reaction temperature of the mixed solution to 90 ℃ and the pH value to 10, stirring the mixed solution in a reactor at a stirring speed of 300 revolutions per minute, keeping the reaction pressure in the reactor at normal pressure, and stirring for 4 hours to perform condensation reaction on the mixed solution to form phenolic resin oil drops.
And then heating the reactor to boil the mixed solution, namely raising the reaction temperature of the mixed solution to the reflux temperature, and continuing stirring at the stirring speed of 300 revolutions per minute for 4 hours to pre-cure phenolic resin oil drops in the mixed solution to form a phenolic resin microsphere matrix.
And finally, taking the phenolic resin microsphere matrix out of the reactor, washing and filtering, placing the phenolic resin microsphere matrix in a 130 ℃ blast drying oven for curing after washing and filtering, and finishing curing after 2 hours to obtain the phenolic resin microspheres with the yield of 65.8%.
Example 6:
firstly, placing raw and auxiliary materials into a reactor for stirring and mixing to obtain a phenolic aldehyde homogeneous phase solution. The raw materials and auxiliary materials comprise the following components in parts by weight: 100 parts of phenolic aldehyde, 45 parts of formaldehyde, 3 parts of alkaline curing agent, 15 parts of surfactant and 600 parts of solvent water. When the raw and auxiliary materials are stirred and mixed, the stirring and mixing speed is 150 rpm, the stirring and mixing time is 30 minutes, the stirring and mixing temperature is 60 ℃, and the reaction pressure in the reactor is normal pressure.
Then, adding a basic catalyst Mg (OH)2Adding the mixture into a phenolic aldehyde homogeneous phase solution to obtain an alkaline mixed solution, adjusting the reaction temperature of the mixed solution to 85 ℃ and the pH value of the mixed solution to 10, stirring the mixed solution in a reactor at a stirring speed of 400 revolutions per minute, keeping the reaction pressure in the reactor at normal pressure, and stirring for 5 hours to perform condensation reaction on the mixed solution to form phenolic resin oil drops.
And then heating the reactor to boil the mixed solution, namely raising the reaction temperature of the mixed solution to the reflux temperature, and continuing stirring at the stirring speed of 400 rpm for 2 hours to pre-cure phenolic resin oil drops in the mixed solution to form a phenolic resin microsphere matrix.
And finally, taking the phenolic resin microsphere matrix out of the reactor, washing and filtering, placing the phenolic resin microsphere matrix in a 130 ℃ blast drying oven for curing after washing and filtering, and finishing curing after 2 hours to obtain the phenolic resin microspheres with the yield of 64.6%.
Example 7:
firstly, placing raw and auxiliary materials into a reactor for stirring and mixing to obtain a phenolic aldehyde homogeneous phase solution. The raw materials and auxiliary materials comprise the following components in parts by weight: 100 parts of phenolic aldehyde, 52 parts of formaldehyde, 5 parts of alkaline curing agent, 20 parts of surfactant and 800 parts of solvent water. When the raw and auxiliary materials are stirred and mixed, the stirring and mixing speed is 200 revolutions per minute, the stirring and mixing time is 10 minutes, the stirring and mixing temperature is 70 ℃, and the reaction pressure in the reactor is normal pressure.
Then, a basic catalyst Ba (OH)2Adding the mixed solution into a phenolic aldehyde homogeneous phase solution to obtain an alkaline mixed solution, adjusting the reaction temperature of the mixed solution to 85 ℃ and the pH value of the mixed solution to 10, stirring the mixed solution in a reactor at a stirring speed of 600 revolutions per minute, keeping the reaction pressure in the reactor at normal pressure, and stirring for 6 hours to enable the mixed solution to perform condensation reaction to form phenolic resin oil drops.
And then heating the reactor to boil the mixed solution, namely raising the reaction temperature of the mixed solution to the reflux temperature, and continuing stirring at the stirring speed of 600 revolutions per minute for 4 hours to pre-cure phenolic resin oil drops in the mixed solution to form a phenolic resin microsphere matrix.
And finally, taking the phenolic resin microsphere matrix out of the reactor, washing and filtering, placing the phenolic resin microsphere matrix in a 120 ℃ blast drying oven for curing after washing and filtering, and finishing curing after 2 hours to obtain the phenolic resin microspheres with the yield of 58.7%.
After the phenolic resin microspheres prepared in the above examples 1 to 7 were carbonized and activated, the corresponding microspherical activated carbon was obtained. The performance of the phenolic resin microspheres and the corresponding microspherical activated carbon of examples 1-7 can now be tested, with the test results shown in table 1.
TABLE 1
As is clear from Table 1, the ash values of the microspherical activated carbons obtained by the carbonization-activation treatment of the phenolic resin microspheres prepared in examples 1 to 7 were used0.2-0.4%, metal content of 14.4-15.8ppm, 16ppm or less, and specific surface area of 1400m2More than/g, the iodine adsorption value is between 1200 and 1400 mg/g. Therefore, after the phenolic resin microspheres prepared by the preparation method of the phenolic resin microspheres are carbonized and activated, the obtained microspherical activated carbon has high purity, low impurity content, higher specific surface area and higher adsorbability.
Claims (10)
1. The preparation method of the phenolic resin microspheres is characterized by comprising the following steps:
step S1: placing phenol, formaldehyde, an alkaline curing agent, a surfactant and solvent water into a reactor, stirring and mixing to obtain a phenolic homogeneous phase solution;
step S2: adding an alkaline catalyst into the phenolic aldehyde homogeneous phase solution to obtain an alkaline mixed solution, adjusting the reaction temperature of the mixed solution to 70-95 ℃, and stirring the mixed solution for condensation reaction to form phenolic resin oil drops;
step S3: raising the reaction temperature of the mixed solution to the reflux temperature, and continuously stirring the mixed solution to pre-cure the phenolic resin oil drops to form a phenolic resin microsphere matrix;
step S4: and taking the phenolic resin microsphere matrix out of the reactor, washing, filtering, and curing in a drying oven to obtain the phenolic resin microspheres.
2. The method of claim 1, wherein in step S1, the alkaline curing agent is urotropin.
3. The method for preparing phenolic resin microspheres according to claim 2, wherein the phenol, the formaldehyde, the alkaline curing agent, the surfactant and the solvent water are mixed in the following weight ratio: the weight portion of the phenol is 100 portions, the weight portion of the formaldehyde is 35-52 portions, the weight portion of the alkaline curing agent is 2-5 portions, the weight portion of the surfactant is 5-20 portions, and the weight portion of the solvent water is 500-900 portions.
4. The method for preparing phenolic resin microspheres as claimed in claim 3, wherein the stirring and mixing speed is 150-200 rpm, the stirring and mixing time is 10-30 minutes, the stirring and mixing temperature is 60-80 ℃, and the stirring and mixing pressure is normal pressure when the phenolic homogeneous solution is obtained by stirring and mixing.
5. The method for preparing phenolic resin microspheres of any one of claims 1-4, wherein in step S2, the alkaline catalyst is KOH, NaOH, ammonia, or K2CO3、Na2CO3、Mg(OH)2Or Ba (OH)2And after the alkaline catalyst is added, the pH value range of the mixed solution is 8-11.
6. The method for preparing phenolic resin microspheres as claimed in claim 5, wherein in the condensation reaction, the stirring speed is 300-600 rpm, the reaction time is 4-6h, the reaction pressure is normal pressure, and the temperature range is 80-90 ℃.
7. The method for preparing phenolic resin microspheres according to claim 6, wherein the temperature range during the condensation reaction is 80-95 ℃.
8. The method for preparing phenolic resin microspheres of claim 7, wherein in the step S3, the pre-curing is performed at a stirring speed of 300-600 rpm, a reaction time of not less than 2h, and a reaction pressure of normal pressure.
9. The method of claim 8, wherein in step S4, the phenolic resin microsphere matrix is washed and filtered at least three times, and the temperature of at least one washing water is higher than 60 ℃.
10. The preparation method of the phenolic resin microspheres as claimed in claim 9, wherein the curing temperature T is not less than 120 ℃ and the curing time T is not less than 2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110864333.9A CN113461883A (en) | 2021-07-29 | 2021-07-29 | Preparation method of phenolic resin microspheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110864333.9A CN113461883A (en) | 2021-07-29 | 2021-07-29 | Preparation method of phenolic resin microspheres |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113461883A true CN113461883A (en) | 2021-10-01 |
Family
ID=77883040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110864333.9A Pending CN113461883A (en) | 2021-07-29 | 2021-07-29 | Preparation method of phenolic resin microspheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113461883A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087561A (en) * | 2020-01-06 | 2020-05-01 | 苏州班顺工业气体设备有限公司 | Powder phenolic resin and production process thereof, prepared carbon molecular sieve and nitrogen making machine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774577A (en) * | 2010-01-08 | 2010-07-14 | 中国林业科学研究院林产化学工业研究所 | Phenolic resin activated carbon microballon and rapid preparation method thereof |
| CN106800661A (en) * | 2017-01-17 | 2017-06-06 | 江苏捷峰高科能源材料股份有限公司 | A kind of preparation method of phenolic resin microspheres |
| CN111777066A (en) * | 2020-08-04 | 2020-10-16 | 上海欧亚合成材料股份有限公司 | Preparation process of phenolic resin-based spherical activated carbon |
| CN111994895A (en) * | 2020-09-08 | 2020-11-27 | 沙县宏盛塑料有限公司 | Phenolic resin carbon microsphere and preparation method and application thereof |
-
2021
- 2021-07-29 CN CN202110864333.9A patent/CN113461883A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774577A (en) * | 2010-01-08 | 2010-07-14 | 中国林业科学研究院林产化学工业研究所 | Phenolic resin activated carbon microballon and rapid preparation method thereof |
| CN106800661A (en) * | 2017-01-17 | 2017-06-06 | 江苏捷峰高科能源材料股份有限公司 | A kind of preparation method of phenolic resin microspheres |
| CN111777066A (en) * | 2020-08-04 | 2020-10-16 | 上海欧亚合成材料股份有限公司 | Preparation process of phenolic resin-based spherical activated carbon |
| CN111994895A (en) * | 2020-09-08 | 2020-11-27 | 沙县宏盛塑料有限公司 | Phenolic resin carbon microsphere and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087561A (en) * | 2020-01-06 | 2020-05-01 | 苏州班顺工业气体设备有限公司 | Powder phenolic resin and production process thereof, prepared carbon molecular sieve and nitrogen making machine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021227603A1 (en) | Microwave ceramic dielectric filter and processing and forming method therefor | |
| CN109364972B (en) | Ruthenium-based composite carbon nitride nano catalyst for lignin depolymerization by hydrogenation, preparation method and application thereof in lignin depolymerization | |
| CN1075539C (en) | Process for preparing phenolic resin base globe activated char | |
| CN113461883A (en) | Preparation method of phenolic resin microspheres | |
| CN110918070A (en) | Biochar-chitosan compound and preparation method and application thereof | |
| CN101157451B (en) | Method for preparing resin-based ball charcoal | |
| CN103936004A (en) | Preparation method of resin-based spherical activated carbon with controllable pore structure | |
| CN113231005B (en) | Method for preparing porous adsorption material without sintering | |
| CN107512902B (en) | Multi-fiber reinforced magnesium-aluminum-carbon refractory material and preparation process thereof | |
| CN110479219B (en) | Porous microsphere foam adsorption material and preparation method thereof | |
| CN111135848B (en) | Wood-based carbon catalyst, preparation method thereof and method for preparing cyclohexanone by phenol hydrogenation | |
| CN101306355B (en) | Method for producing macro-porous cellulose composite expansion bed substrate using direct dilution method | |
| CN111439823A (en) | Modified coconut coir-loaded nano zero-valent iron composite material, and preparation method and application thereof | |
| CN111171345A (en) | Preparation method of polyamide microspheres | |
| CN111943198A (en) | Preparation method of coconut shell carbon molecular sieve with high specific surface area | |
| CN113788509A (en) | Water treatment chitosan mixture and preparation method thereof | |
| CN112679225A (en) | Porous ceramic material pore-forming agent and preparation method thereof | |
| CN117299091B (en) | Humic acid functionalized carbon submicron sphere, preparation method thereof and application thereof in heavy metal contaminated soil regeneration | |
| CN110711576B (en) | Method for preparing palladium-based catalyst by pulling method and application | |
| CN112974827A (en) | Preparation method of spherical silver powder with high tap density and surface wrinkles | |
| CN112480714B (en) | Surface modification method of nano calcium carbonate with particle size less than 20nm | |
| KR20200055985A (en) | Method for manufacturing high-efficiency activated carbon for removal of harmful gas using nano metal powder | |
| CN111892052A (en) | Method for repairing and regulating aperture of activated carbon | |
| CN112548099B (en) | Method for preparing near-spherical pore porous alloy by using ammonium bicarbonate as pore-forming agent | |
| CN111943194A (en) | Preparation method of coconut shell carbon molecular sieve for methane purification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211001 |