COMBINED TREATMENT DEVICE AND METHOD FOR SURFACE MODIFICATION OF FUMED SILICA
20220389228 · 2022-12-08
Assignee
- GUANGZHOU HUIFU RESEARCH INSTITUTE CO., LTD. (Guangdong, CN)
- HUBEI HUIFU NANOMATERIAL CO., LTD. (Hubei, CN)
Inventors
- Xianjian DUAN (Guangdong, CN)
- Chunlei WU (Guangdong, CN)
- Yuelin WANG (Guangdong, CN)
- Shiyu XU (Guangdong, CN)
- Chenggang WANG (Hubei, CN)
Cpc classification
B01D45/16
PERFORMING OPERATIONS; TRANSPORTING
C01B33/14
CHEMISTRY; METALLURGY
B01D50/20
PERFORMING OPERATIONS; TRANSPORTING
B01J8/26
PERFORMING OPERATIONS; TRANSPORTING
B01D46/02
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01D45/16
PERFORMING OPERATIONS; TRANSPORTING
B01D46/02
PERFORMING OPERATIONS; TRANSPORTING
B01D50/20
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The present disclosure relates to a combined treatment method for surface modification of fumed silica, which comprises the following steps: (1) two sets of modification devices are used to jointly treat fumed silica; the fumed silica is modified with a modifier in the reaction furnace of each set of modification devices to obtain two groups of modified fumed silica and exhaust gas respectively; (2) the exhaust gas obtained in step (1) is separated respectively to obtain unreacted modifier and by-products, and the obtained by-products are input into the reaction furnace of the other set of modification devices as reaction assistants to participate in the modification reaction; and the obtained unreacted modifiers are returned to the reaction furnace of the original modification device for repeated use.
Claims
1. A combined treatment method for surface modification of fumed silica, comprising the following steps: step (1) two sets of modification devices are used to jointly treat fumed silica, each of which includes a reaction furnace and a gas separator; the fumed silica is treated with a modifier in the reaction furnace of each set of modification devices, and two groups of modified fumed silica and exhaust gas are obtained respectively; step (2) the exhaust gas obtained in the step (1) is separated respectively to obtain unreacted modifier and by-products; and the obtained by-products are input into the reaction furnace of the other set of modification devices as reaction assistants to participate in the modification reaction; and the obtained unreacted modifiers are returned to the reaction furnace of the original modification devices for repeated use; wherein, the modifiers used in the two sets of modification devices are different from each other and are selected from organochlorosilanes, alkylsiloxanes, alkylsilazanes, hydroxyl-terminated polysiloxanes and cyclosiloxanes; wherein, the modifiers used in the two sets of modification devices are not both selected from hydroxyl-terminated polysiloxanes or cyclosiloxanes.
2. The combined treatment method for surface modification of fumed silica according to claim 1, wherein a structural formula of the organochlorosilane is R.sub.m.sup.1SiCl.sub.4-m; a structural formula of the alkylsiloxane is R.sub.m.sup.2Si(OR.sup.3).sub.4-m; a structural formula of the alkylsilazane is ##STR00008## a structural formula of the hydroxyl-terminated polysiloxanes is ##STR00009## a structural formula of the cyclosiloxane is ##STR00010## wherein, R.sup.1, R.sup.3 are independently selected from C1˜C6 alkyl; R.sup.2 is selected from C1˜C22 alkyl; R.sup.4, R.sup.5 are independently selected from C1˜C6 alkyl, C2˜C6 alkenyl or benzene; each R6, R7 is independently selected from H, C1˜C6 alkyl or C2˜C6 alkenyl; m is independently selected from the natural numbers from 1 to 3, n is selected from the natural numbers from 3 to 30, and o is selected from the natural numbers from 3 to 6.
3. The combined treatment method for surface modification of fumed silica according to claim 2, wherein, R.sup.1 and R.sup.3 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl or n-hexyl; R.sup.2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl or C7˜C16 alkyl; R.sup.4 and R.sup.5 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, hexyl, vinyl, propenyl or phenyl; each R.sup.6, R.sup.7 is independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, hexyl, vinyl, propenyl, butene or pentenyl; m is independently selected from 1, 2 or 3, n is selected from a natural number from 3 to 20, and o is selected from 3, 4, 5 or 6.
4. The combined treatment method for surface modification of fumed silica according to claim 3, wherein, the organochlorosilane is selected from dimethyldichlorosilane or trimethylchlorosilane; the alkylsiloxane is selected from dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane or diethyldiethoxysilane; the hydroxyl-terminated polysiloxane is selected from hydroxyl-terminated polydimethylsiloxane, hydroxyl-terminated polymethylvinylsiloxane or hydroxyl-terminated polymethylphenylsiloxane; the cyclosiloxane is selected from hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane or dodecamethylcyclohexasiloxane.
5. The combined treatment method for surface modification of fumed silica according to claim 1, wherein the modifier used in one set of the modification devices is organochlorosilane, and the modifier used in the other set of the modification devices is alkylsiloxane, alkylsilazane, hydroxyl terminated polysiloxane or cyclosiloxane; or the modifier used in one set of the modification devices is alkylsiloxane, and the modifier used in the other set of the modification devices is alkylsilazane, hydroxyl-terminated polysiloxane. oxane or cyclosiloxane; or the modifier used in one set of the modification devices is alkylsilazane, and the modifier used in the other set of the modification devices is hydroxyl terminated polysiloxane or cyclosiloxane alkyl.
6. The combined treatment method for surface modification of fumed silica according to claim 1, wherein, the process of separating the exhaust gas in the step (2) includes: separating the powder and gas in the exhaust gas once, returning the powder obtained by the first separation to the reaction furnace of the original modification devices to continue the modification reaction; filtering the gas obtained from the first separation; the gas obtained from the filtration is separated through gas separation into the unreacted modifiers and by-products, and the powder obtained by the filtration is returned for the primary separation.
7. The combined treatment method for surface modification of fumed silica according to claim 1, wherein, in the step (1), under fluidization of inert gas, the vaporized modifier is contacted and reacted with the fumed silica; by adjusting a flow rate of the inert gas, a time for the powder passing through the reaction furnace is maintained for 10-60 minutes.
8. The combined treatment method for surface modification of fumed silica according to claim 1, wherein, in each set of modification devices, a raw material mass ratio of the fumed silica and the modifier is 25-35:1-7; and the reaction temperature of the modification reaction is 100° C.-350° C.
9. The combined treatment method for surface modification of fumed silica according to claim 1, wherein the exhaust gas in the step (1) is input into a gas separator for gas separation to obtain unreacted modifiers and by-products; the obtained unreacted modifiers are returned to the reaction furnace of the original modification devices for repeated use; the obtained by-products are input into the reaction furnace of the other set of modification devices as reaction assistants to participate in the modification reaction.
10. The combined treatment method for surface modification of fumed silica according to claim 9, wherein each set of modification devices further include a separation member; before the exhaust gas is input into the gas separator, it is first input into the separation member to separate the powder and gas, and the separated powder is returned to the reaction furnace of the original modification devices to be modified again, and the separated gas is input into the gas separator for gas separation.
11. The combined treatment method for surface modification of fumed silica according to claim 10, wherein the separation member includes a cyclone separator and a bag filter; before the exhaust gas is input into the gas separator, it is firstly input into the cyclone separator for primary separation, the powder obtained from the primary separation is returned to the reaction furnace of the original modification devices for further modification, and the gas obtained from the primary separation is input into the bag filter for filtration; the gas obtained from the filtration is input into the gas separator for gas separation, and the powder obtained from the filtration is returned to the cyclone separator for the primary separation.
12. The combined treatment method for surface modification of fumed silica according to claim 9, wherein each set of modification devices includes at least two series-connected reaction furnaces; the fumed silica and the modifier are first subjected to a modification reaction in a first reaction furnace, and the fumed silica powder discharged from the first reaction furnace is then input into a second reaction furnace to continue the modification reaction; the unreacted modifier obtained by separation in the step (2) is vaporized and returned to the second reaction furnace of the original modification devices for repeated use; the by-products obtained by separation in the step (2) are input into the first reaction furnace of the other set of modification devices as reaction assistants to participate in the modification reaction.
13. The combined treatment method for surface modification of fumed silica according to claim 12, wherein each set of the modification devices includes three series-connected reaction furnaces, and the fumed silica powder discharged from the second reaction furnace is input into a third reaction furnace to continue the modification reaction.
14. A combined treatment device for surface modification of fumed silica, comprising two sets of modification devices, each set of modification devices includes a reaction furnace and a gas separator, wherein, the reaction furnace includes a first inlet, a second inlet, a first outlet for discharging powder and a second outlet for discharging exhaust gas, the second outlet is communicated with an inlet of the gas separator; an outlet of the gas separator of a first set of modification devices communicated with the first inlet of the reaction furnace of a second set of modification devices; the outlet of the gas separator of the second set of modification devices is communicated with the first inlet of the reaction furnace of the first set of modification devices.
15. The combined treatment device for surface modification of fumed silica according to claim 14, wherein each set of modification devices further comprises a feeding tank, and an outlet of the feeding tank is communicated with the first inlet.
16. The combined treatment device for surface modification of fumed silica according to claim 14, wherein each set of modification devices further comprises a venturi tube, and the powder enters the first inlet through the venturi tube.
17. The combined treatment device for surface modification of fumed silica according to claim 14, wherein each set of modification devices further comprises a gasifier, and an outlet of the gasifier is communicated with the second inlet.
18. The combined treatment device for surface modification of fumed silica according to claim 14, wherein each set of modification devices further comprises a separation member, which includes a first separation outlet and a second separation outlet, the second outlet is communicated with the inlet of the separation member, the first separation outlet is communicated with the first inlet, and the second separation outlet is communicated with the inlet of the gas separator.
19. The combined treatment device for surface modification of fumed silica according to claim 18, wherein the separation member includes a cyclone separator and a bag filter, the cyclone separator includes a first cyclone outlet and a second cyclone outlet, and the bag filter includes a first filter outlet and a second filter outlet; an inlet of the cyclone separator is communicated with the second outlet, and the first cyclone outlet is communicated with the first inlet to form the first separation outlet; the second cyclone outlet is communicated with an inlet of the bag filter, the first filter outlet is communicated with the inlet of the cyclone separator, and the second filter outlet is communicated with the inlet of the gas separator to form the second separation outlet.
20. The combined treatment device for surface modification of fumed silica according to claim 18, wherein the outlet of the gas separator comprises a gas outlet and a liquid outlet, and the liquid outlet is communicated with the second inlet; the gas outlet of the first set of modification devices is communicated with the first inlet of the reaction furnace of the second set of modification devices; the gas outlets of the second set of modification devices is communicated with the first inlets of the reaction furnace of the first set of modification devices.
21. The combined treatment device for surface modification of fumed silica according to claim 20, wherein each set of modification devices further comprises a modifier storage tank, which is communicated with the liquid outlet.
22. The combined treatment device for surface modification of fumed silica according to claim 20, wherein each set of modification devices comprises at least two reaction furnaces, and each of the reaction furnaces is provided with at least two first inlets; the first outlet of the first reaction furnace is communicated with one of the first inlet of the second reaction furnace; the first separation outlet of the separation piece is communicated with another first inlet of the second reaction furnace; the liquid outlet of the gas separator is communicated with the second inlet of the second reaction furnace; the gas outlet of the first set of modification devices is communicated with one of the first inlets of the first reaction furnace of the second set of modification devices; the gas outlet of the second set of modification devices is communicated with one of the first inlets of the first reaction furnace of the first set of modification devices.
23. The combined treatment device for surface modification of fumed silica according to claim 22, wherein each set of the modification devices comprises three reaction furnaces, and the first outlet of the second reaction furnace is communicated with one of the first inlets of the third reaction furnace, and the first outlet of the third reaction furnace forms a product discharge port; each second outlet of the three reaction furnaces are all communicated with the inlets of the separation members.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0069] The drawings here show specific examples of the technical solutions of the present disclosure, form a part of the specification together with the specific embodiments, and are used to explain the technical solutions, principles and effects of the present disclosure.
[0070] Unless specified or otherwise defined, in different drawings, the same reference numerals represent the same or similar technical features, and the same or similar technical features may also be represented by different reference numerals.
[0071]
[0072]
[0073]
[0074]
[0075]
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DESCRIPTION OF REFERENCE SIGNS
[0078] 10, reaction furnace; 11, first inlet; 12, second inlet; 13, first outlet; 14, second outlet; 20, gas separator; 21, gas outlet; 22, liquid outlet; 30, modifier storage tank; 40, feeding tank; 50, venturi tube; 60, gasifier; 70, separation member; 71, first separation outlet; 72, second separation outlet; 73, cyclone separator; 731, first Cyclone outlet; 732, second cyclone outlet; 74, bag filter; 741, first filter outlet; 742, second filter outlet.
DESCRIPTION OF THE EMBODIMENTS
[0079] To make the present disclosure easy to understand, a more comprehensive description of the present disclosure will be given below with reference to the figures of the specification and embodiments. The preferred embodiments of the present disclosure are given below. However, the present disclosure may be acquired in many different ways, and is not limited to the embodiments as described here. These embodiments are provided so that the content disclosed by the present disclosure may be more thoroughly and comprehensively understood.
[0080] Unless otherwise defined, all technical and scientific terms as used herein have the same meanings as those usually understood by a person skilled in the art of the present disclosure. The terms used in the description of the present disclosure are for description of the specific embodiments only and are not intended to limit the present disclosure. The term “and/or” as used herein includes any or all combinations of one or more relevant listed items. In the case of combining the technical solutions of the present disclosure with realistic scenarios, all technical and scientific terms used herein may also have meanings corresponding to achieving the purposes of the technical schemes of the present disclosure.
[0081] Unless specifically stated or otherwise defined, “first, second . . . ” used in the description is only used to distinguish names, and does not represent a specific number or order.
[0082] It should be noted that when a component is considered to be “secured” to another component, it can be directly secured to said another component, or it can be secured to said another component through a centered component; when a component is considered to be “connected” to another component, it can be directly connected to said another component, or be connected to said another component through a centered component at the same time; When a component is considered to be “installed on” another component, it can be directly installed on said another component, or be installed on said another component through a centered component at the same time; When an component is considered to “set on” another component, it can be directly set on said another component, or be set on said another component through a central component at the same time.
[0083] This embodiment provides a combined treatment method for surface modification of hydrophilic fumed silica, comprising the following steps:
[0084] (1) Two sets of modification devices are used to jointly treat fumed silica, each set of devices includes a reaction furnace and a gas separator; the fumed silica is modified with a modifier in the reaction furnace of each set of modification devices, and two groups of modified fumed silica and exhaust gas are obtained respectively;
[0085] (2) The exhaust gas obtained in step (1) is separated respectively to obtain unreacted modifier and by-products, and the obtained by-products are input into the reaction furnace of the other set of modification devices to participate in the modification reaction as reaction assistants, and the obtained unreacted modifier is returned to the reaction furnace of the original modification device for repeated use;
[0086] the modifiers used in the two sets of modification devices are different from each other and are selected from organochlorosilanes, alkylsiloxanes, alkylsilazanes, hydroxyl-terminated polysiloxanes and cyclosiloxanes; wherein, the modifiers used in the two sets of modification devices are not all selected from hydroxyl-terminated polysiloxanes or cyclosiloxanes.
[0087] The combined treatment device for surface modification used in the combined treatment method for surface modification is shown in
[0088] The fumed silica powder to be modified is introduced into the two sets of modification devices through the first inlet 11, and then different modifiers are introduced through the second inlet 12. The carrier gas is introduced into the reaction furnace 10, and the fumed silica reacts with the modifier in the reaction furnace 10 for the surface modification of the fumed silica. After the reaction, the fumed silica powder is discharged through the first outlet 13. At this time, the surface modification of the fumed silica is completed, and the collection treatment is performed. The exhaust gas is discharged through the second outlet 14, and then enters the gas separator 20, which separates the unreacted modifier and the by-products after the modification, wherein the by-products are vaporized and discharged through the outlet of the gas separator 20. The by-products of the first set of modification devices enter the reaction furnace 10 of the second set of modification devices, and the by-products of the second set of modification devices enter the reaction furnace 10 of the first set of modification devices.
[0089] Specifically, the structural formula of the organochlorosilane is R.sub.m.sup.1SiCl.sub.4-m; the structural formula of the alkylsiloxane is R.sub.m.sup.2Si(OR.sup.3).sub.4-m; the structural formula of the alkylsilazane is
##STR00004##
the structural formula of the hydroxyl-terminated polysiloxanes is
##STR00005##
the structural formula of the cyclosiloxane is
##STR00006##
[0090] wherein,
[0091] R.sup.1 and R.sup.3 are independently selected from C1˜C6 alkyl;
[0092] R.sup.2 is selected from C1˜C22 alkyl;
[0093] R.sup.4 and R.sup.5 are independently selected from C1˜C6 alkyl, C2˜C6 alkenyl or C4˜C8 aryl;
[0094] each R.sup.6 and R.sup.7 is independently selected from H, C1˜C6 alkyl or C2˜C6 alkenyl;
[0095] m is independently selected from the natural numbers of 1 to 3; n is selected from the natural numbers of 3 to 30; and o is selected from the natural numbers of 3 to 6.
[0096] In the present disclosure, the by-products (main components of tail gas) generated by different modifiers in the modification reaction process are different. The by-products produced by organochlorosilane as modifiers are mainly HCl (as shown in formula (1)); the by-products produced by alkylsiloxanes as modifiers are mainly alcohols (as shown in formula (2)); the by-products produced by alkylsilazane as modifiers are mainly NH3 (as shown in formula (3)); the by-products produced by hydroxyl-terminated polysiloxane or cyclosiloxane as modifiers are mainly H.sub.2O (as shown in formula (4) and formula (5)). Refer to the following formulas:
##STR00007##
[0097] The inventors of the present disclosure found that, in the two sets of modification devices connected in parallel, when two different types of modifiers are selected from the above four types of modifiers to cooperate with each other, the by-products generated by one set of modification devices are input into the other set of modification devices. On one aspect, zero emission and zero pollution can be achieved, which greatly reduces the treatment cost of by-products; on the other aspect, the by-products of one set of modification devices can be used as the reaction assistants for the other set of modification devices, promoting the modification reaction in the other set of modification devices through various mechanisms, which ultimately improves the reaction efficiency and product quality. The specific mechanisms include at least: (1) By-products H.sub.2O, HCl, NH.sub.3 and alcohols can improve the reactivity of silanols and activate them, thereby promoting the reaction between organosilanes and silanols. (2) If the modifier is organochlorosilane, the produced HCl will be adsorbed on the surface of the powder. While the by-products alcohols, NH.sub.3, H.sub.2O and HCl of the modifiers, such as alkyl siloxane, alkyl silazane, and hydroxy-terminated siloxane, can help to remove the adsorption of HCl on the surface of the powder which improves the actual contact area between the powder and the reactant as well as the purity of the powder. In practical applications, it shows that the increase of pH value of the finished products may help to reduce the energy consumption of desorption. (3) When the modifier of one set of modification devices is alkylsiloxane, hydroxyl-terminated polysiloxane or cyclosiloxane, the modifier of the other set of modification devices is organochlorosilane. Alcohols or H.sub.2O, the by-products of one set of modification devices can be used as reaction assistants to undergo hydrolysis or alcoholysis with organochlorosilane, the modifier of the other set of modification devices. The obtained intermediates are dehydrated or dealcoholized with fumed silica, which promotes the modification reaction of the other set of modification devices and improves the reaction efficiency. In practical applications, it shows that the amount of modifier can be reduced, or when at the same amount, the modification efficiency of the finished product is improved (the carbon content is increased).
[0098] For example, when the modifier introduced into the first set of modification devices is dimethyldichlorosilane, and the modifier introduced into the second set of modification devices is hexamethyldisilazane, the by-products generated by the reaction of the two modifiers with the silanols on the surface of fumed silica are hydrogen chloride and ammonia, respectively. Its advantages include at least: (1) The by-products hydrogen chloride and ammonia generated by the two reactions can mutually promote the reaction between each other's modifier and silanol (i.e. hydrogen chloride can promote the reaction between hexamethyldisilazane and silanol; while ammonia can promote the reaction of dimethyldichlorosilane with silanol); (2) The two by-products can also promote the removal of by-products in the reaction process of each other, and therefore reduce the concentration of by-products in the reaction process. That is, the hydrogen chloride generated by the first set of modification devices is in the reaction furnace 10, and reacts with the ammonia gas generated in the second set of modification devices to produce ammonium chloride; the ammonia gas generated by the second set of modification devices is in the reaction furnace 10, and reacts with the hydrogen chloride produced in the first set of modification devices to produce ammonium chloride. The combined treatment device for surface modification not only improves the efficiency of the surface modification reaction of fumed silica, but also enables different by-products to react with each other, thereby reducing the difficulty of treatment for by-products. Moreover, the content of by-products in the reaction system is reduced, and therefore the progress of the positive modification reaction is promoted.
[0099] When the fumed silica powder is transported, nitrogen is used as a carrier gas, which is introduced into the reaction furnace 10 as a carrier gas and a protective gas, which enables the fumed silica powder to be fluidized and react with the modifiers. The dotted lines in
[0100] As shown in
[0101] As shown in
[0102] As shown in
[0103] Wherein, two pipes are provided on the gas outlet 21, and each pipe is provided with a valve, one of which is a by-products discharging pipe connected to another set of modification devices, and the other is a nitrogen discharging pipe. Shut off the by-products discharging pipeline, and then separate and discharge nitrogen through the gas separator 20. At this time, only nitrogen can be discharged; similarly, shut off the nitrogen discharge pipeline and only by-products can be discharged into the reaction furnace 10 of another set of reforming devices through the separation of the gas separator 20.
[0104] As shown in
[0105] As shown in
[0106] As shown in
[0107] As shown in
[0108] As shown in
[0109] In the same set of modification devices, the raw fumed silica powder and the modifiers carry out modification reaction in the first reaction furnace 10. After the reaction in the first reaction furnace 10, there will still be a lot of unreacted fumed silica powder. The fumed silica in the first reaction furnace 10 is discharged through the first outlet 13, then it enters into the second reaction furnace 10 through the first inlet 11 of the second reaction furnace 10, while the recycled fumed silica powder is also introduced into the other first inlet 11 of the second reaction furnace 10, and the unreacted fumed silica powder in the second reaction furnace 10 further fully reacts with the unreacted modifiers introduced through the second inlet 12. Therefore, not only the unreacted modifiers are fully utilized, but also the unreacted fumed silica in the first reaction furnace 10 is fully modified, and moreover, the feed ratio of the modifiers and fumed silica in the two reaction furnaces is kept constant. Meanwhile, the by-products of the second set of modification devices are passed into the first reaction furnace 10 of the first set of modification devices. As the first reaction furnace 10 is the starting point of the modification reaction, and the reaction produces the most by-products, so a reaction assistant is more needed to play its role to remove the by-products and promote the positive modification reaction.
[0110] As shown in
[0111] Recycling and re-reaction of the fumed silica powder and the modifiers, helps to control the sufficient reaction between the fumed silica and the modifiers. As the fumed silica powder and the modifiers are recycled until they are completely reacted, the reaction is completed approximately 100%. When the input of fumed silica and modifier is controlled, the ratio of fumed silica and modifiers in each set of modification devices can be stabilized. So, the stability of product quality can be achieved, and moreover, the raw materials can be fully utilized.
[0112] The following first reaction furnace 10 refers to the first reaction furnace where the unsurface-modified fumed silica is passed; The second reaction furnace 10 refers to the one where the fumed silica modified by the first reaction furnace 10 is passed; The third reaction furnace 10 refers to the one where the fumed silica after being modified by the second reaction furnace 10 is passed.
[0113] In this embodiment, the transportation of the fumed silica powder is all conveyed through the venturi tube 50.
[0114] Wherein: The aforementioned “first, second, third . . . ” does not represent a specific number and order, but is only used to distinguish names.
[0115] As each set of modification devices mentioned above is the same, only one set devices is described when describing the internal structure of the modification devices.
[0116] The method of the present disclosure will be further described below in conjunction with specific embodiments.
[0117] The following “1-1 furnace” refers to the first reaction furnace of the first set of modification devices; the “1-2 furnace” refers to the second reaction furnace of the first set of modification devices; the “1-3 furnace” refers to the third reaction furnace of the first set of modification devices; the “2-1 furnace” refers to the first reaction furnace of the second set of modification devices; the “2-2 furnace” refers to the second reaction furnace of the second set of modification devices; the “2-3 furnaces” refers to the third reaction furnace of the second set of modification devices;
Example 1
[0118] In the parallel-connected modification devices shown in
TABLE-US-00001 TABLE 1 Raw material ratio and main process parameters in Example 1. Device Hydrophobic Modification Device 1 Hydrophobic Modification Device 2 Raw Material SiO.sub.2 DMDC N.sub.2 SiO.sub.2 HMDS N.sub.2 Feed rate 30 kg/h 2.2 kg/h 75 kg/h 30 kg/h 2.5 kg/h 75 kg/h Process Furnace Furnace Furnace Furnace Furnace Furnace parameters 1-1 1-2 1-3 2-1 2-2 2-3 Temperature 100-180 130-200 180-250 150-200 180-250 220-300 (° C.) Product I-1 I-2
Example 2
[0119] In the parallel-connected modification devices shown in
TABLE-US-00002 TABLE 2 Raw material ratio and main process parameters in Example 2. Device Hydrophobic Modification Device 1 Hydrophobic Modification Device 2 Raw Material SiO.sub.2 DMDC N.sub.2 SiO.sub.2 DMDS N.sub.2 Feed rate 30 kg/h 2.2 kg/h 75 kg/h 30 kg/h 2.1 kg/h 78 kg/h Process Furnace Furnace Furnace Furnace Furnace Furnace parameters 1-1 1-2 1-3 2-1 2-2 2-3 Temperature 100-180 130-200 180-250 120-200 150-220 200-300 (° C.) Product II-1 II-2
Example 3
[0120] In the parallel-connected modification devices shown in
TABLE-US-00003 TABLE 3 Raw material ratio and main process parameters in Example 3 Device Hydrophobic Modification Device 1 Hydrophobic Modification Device 2 Raw Material SiO.sub.2 DMDC N.sub.2 SiO.sub.2 PDMS N.sub.2 Feed rate 30 kg/h 2.2 kg/h 75 kg/h 30 kg/h 5 kg/h 82 kg/h Process Furnace Furnace Furnace Furnace Furnace Furnace parameters 1-1 1-2 1-3 2-1 2-2 2-3 Temperature 100-180 130-200 180-250 180-250 200-280 250-350 (° C.) Product III-1 III-2
Example 4
[0121] In the parallel-connected modification devices shown in
TABLE-US-00004 TABLE 4 Raw material ratio and main process parameters in Example 4 Device Hydrophobic Modification Device 1 Hydrophobic Modification Device 2 Raw Material SiO.sub.2 PDMS N.sub.2 SiO.sub.2 HMDC N.sub.2 Feed rate 30 kg/h 5 kg/h 82 kg/h 30 kg/h 2.5 kg/h 75 kg/h Process Furnace Furnace Furnace Furnace Furnace Furnace parameters 1-1 1-2 1-3 2-1 2-2 2-3 Temperature 180-250 200-280 250-350 150-200 180-250 220-300 (° C.) Product IV-1 IV-2
Example 5
[0122] In the parallel-connected modification devices shown in
TABLE-US-00005 TABLE 5 Raw material ratio and main process parameters in Example 5 Device Hydrophobic Modification Device 1 Hydrophobic Modification Device 2 Raw Material SiO.sub.2 DMDS N.sub.2 SiO.sub.2 HMDS N.sub.2 Feed rate 30 kg/h 2.1 kg/h 78 kg/h 30 kg/h 2.5 kg/h 75 kg/h Process Furnace Furnace Furnace Furnace Furnace Furnace parameters 2-1 2-2 2-3 2-1 2-2 2-3 Temperature 120-200 150-220 200-300 150-200 180-250 220-300 (° C.) Product V-1 V-2
Comparative Example 1
[0123] The parallel-connected modification structure devices are also used, each set as an independent fumed silica hydrophobic modification device. Wherein, the hydrophobic modifier of the first set of modification devices is Hydroxy-terminated polydimethylsiloxane (PDMS), and the hydrophobic modifier of the second set of modification devices is Hexamethyldisilazane (HMDS); the specific surface area of hydrophilic fumed silica is 200 m.sup.2/g, and the carrier gas is nitrogen. By adjusting the flow rate of nitrogen, the time for the powder to pass through the reaction furnace is maintained for 10˜60 mins. The ratio of the respective raw materials and the main process parameters are shown in Table 6. The difference from
TABLE-US-00006 TABLE 6 Raw material ratio and main process parameters in Comparative Example 1 Device Hydrophobic Modification Device 1 Hydrophobic Modification Device 2 Raw Material SiO.sub.2 PDMS N.sub.2 SiO.sub.2 HMDS N.sub.2 Feed rate 30 kg/h 6.2 kg/h 75 kg/h 30 kg/h 2.5 kg/h 75 kg/h Process Furnace Furnace Furnace Furnace Furnace Furnace parameters 1-1 1-2 1-3 2-1 2-2 2-3 Temperature 200-250 230-320 300-380 150-200 180-250 220-300 (° C.) Product C-1 C-2
Comparative Example 2
[0124] The parallel-connected modification structure devices are also used, each set as an independent fumed silica hydrophobic modification device. Wherein, the hydrophobic modifier of the first set of modification devices is Hydroxy-terminated polydimethylsiloxane (PDMS), and the hydrophobic modifier of the second set of modification devices is Dimethyldimethoxysilane (DMDS); the specific surface area of hydrophilic fumed silica is 200 m.sup.2/g, and the carrier gas is nitrogen. By adjusting the flow rate of nitrogen, the time for the powder to pass through the reaction furnace is maintained for 10˜60 mins. The ratio of the respective raw materials and the main process parameters are shown in Table 7. The difference from
TABLE-US-00007 TABLE 7 Raw material ratio and main process parameters in Comparative Example 2 Device Hydrophobic Modification Device 1 Hydrophobic Modification Device 2 Raw Material SiO.sub.2 PDMS N.sub.2 SiO.sub.2 DMDS N.sub.2 Feed rate 30 kg/h 6.2 kg/h 75 kg/h 30 kg/h 3.2 kg/h 72 kg/h Process Furnace Furnace Furnace Furnace Furnace Furnace parameters 1-1 1-2 1-3 2-1 2-2 2-3 Temperature 200-250 230-320 300-380 180-250 200-300 250-350 (° C.) Product C-3 C-4
Comparative Example 3
[0125] The parallel-connected modification structure devices are also used, each set as an independent fumed silica hydrophobic modification device. Wherein, the hydrophobic modifier of the first set of modification devices is dimethyldichlorosilane (DMDC), and the hydrophobic modifier of the second set of modification devices is Hexamethyldisilazane (HMDC); The specific surface area of hydrophilic fumed silica is 200 m.sup.2/g, and the carrier gas is nitrogen. By adjusting the flow rate of nitrogen, the time for the powder to pass through the reaction furnace is maintained for 10˜60 mins. The ratio of the respective raw materials and the main process parameters are shown in Table 8. The material flow of each set of modification devices is shown in
TABLE-US-00008 TABLE 8 Raw material ratio and main process parameters in Comparative Example 3 Device Hydrophobic Modification Device 1 Hydrophobic Modification Device 2 Raw Material SiO.sub.2 DMDC N.sub.2 SiO.sub.2 HMDS N.sub.2 Feed rate 30 kg/h 3.2 kg/h 72 kg/h 30 kg/h 3 kg/h 75 kg/h Process Furnace Furnace Furnace Furnace Furnace Furnace parameters 1-1 1-2 1-3 2-1 2-2 2-3 Temperature 180-250 200-300 250-350 150-200 180-250 220-300 (° C.) Product C-5 C-6
[0126] The technical indexes of the example samples, comparative examples samples are as shown in table 9.
TABLE-US-00009 TABLE 9 Samples Technical Indexes carbon content Volatile matter at Sample No. pH Value (%) 105° C. (%) I-1 5.2 1.23 0.35 I-2 6.2 1.70 0.25 II-1 4.7 1.27 0.40 II-2 5.5 1.33 0.32 III-1 4.2 1.18 0.37 III-2 5.8 4.90 0.42 IV-1 6.6 5.20 0.35 IV-2 6.5 1.75 0.20 V-1 5.9 1.35 0.32 V-2 6.7 1.72 0.23 C-1 5.6 4.20 0.33 C-2 7.2 1.45 0.38 C-3 6.2 4.40 0.45 C-4 5.0 1.22 0.42 C-5 4.2 1.05 0.32 C-6 6.9 1.50 0.27 Test method: GB/T 20020-2013.
[0127] The specific conditions and parameters of the auxiliary gas of each set of devices in the examples and comparative examples are compared as follows:
TABLE-US-00010 TABLE 10 DMDC modification Volatile carbon matter SiO.sub.2 DMDC N.sub.2 Temperature (° C.) pH content at105° C. Auxiliary (kg/h) (kg/h) (kg/h) Furnace-1 Furnace-2 Furnace-3 value (%) (%) gas I-1 30 2.2 75 100-180 130-200 180-250 5.2 1.23 0.35 NH.sub.3 II-1 30 2.2 75 100-180 130-200 180-250 4.7 1.27 0.4 CH.sub.3OH III-1 30 2.2 75 100-180 130-200 180-250 4.2 1.18 0.37 H.sub.2O C-5 30 3.2 72 180-250 200-300 250-350 4.2 1.05 0.32 none
[0128] From the results in Table 10, it can be seen that the reaction conditions and raw material ratios of samples I-1˜III-1 are the same, while the auxiliary gas used is different, and the carbon content, pH value, and volatile matter at 105° C. of the modified products are different. In the reaction of DMDC and silica, the by-products H.sub.2O, NH.sub.3 and CH.sub.3OH are beneficial to the reaction and the removal of HCl. Compared with C-5, it is found that the amount of modifier DMDC in C-5 is 45% higher than that of others, and the amount of carrier gas is also lower (slow flow rate, long reaction time). The reaction temperature is higher, but the carbon content of the modified product is low, and the pH value is also low, indicating that the reaction efficiency is lower than that of other examples.
TABLE-US-00011 TABLE 11 HMDS modification Volatile carbon matter SiO.sub.2 HMDS N.sub.2 Temperature (° C.) pH content at 105° C. Auxiliary (kg/h) (kg/h) (kg/h) Furnace-1 Furnace-2 Furnace-3 value (%) (%) gas I-2 30 2.5 75 150-200 180-250 220-300 6.2 1.7 0.25 HCl IV-2 30 2.5 75 150-200 180-250 220-300 6.5 1.75 0.2 H.sub.2O V-2 30 2.5 75 150-200 180-250 220-300 6.7 1.72 0.23 CH.sub.3OH C-2 30 2.5 75 150-200 180-250 220-300 7.2 1.45 0.38 none C-6 30 3 75 150-200 180-250 220-300 6.9 1.5 0.27 none
[0129] It can be seen from Table 11 that the test conditions of I-2, IV-2, V-2 and C-2 are the same, but the auxiliary gas is different, wherein C-2 has no auxiliary gas; and C-6 has no auxiliary gas, and the amount of modifier HMDS is 20% higher. However, from the results, the auxiliary gas is conducive to the progress of the reaction (high carbon content), and is also conducive to the removal of by-product NH3 (low pH value).
TABLE-US-00012 TABLE 12 PDMS modification Volatile Carbon matter SiO.sub.2 PDMS N.sub.2 Temperature (° C.) pH content at 105° C. Auxiliary (kg/h) (kg/h) (kg/h) Furnace-1 Furnace-2 Furnace-3 value (%) (%) gas III-2 30 5 82 180-250 200-280 250-350 5.8 4.9 0.42 HCl IV-1 30 5 82 180-250 200-280 250-350 6.6 5.2 0.35 NH.sub.3 C-1 30 6.2 75 200-250 230-320 300-380 5.6 4.2 0.33 None C-3 30 6.2 75 200-250 230-320 300-380 6.2 4.4 0.45 none
[0130] As shown in Table 12, the amount of C-1 and C-3 modifier is 20% higher, and the amount of nitrogen is 8.5% lower, and the reaction temperature is also higher, but the carbon contents are over 10% lower than that of III-2 and Iv-1, which shows that both HCl and HN.sub.3 can promote the modification reaction and improve the reaction efficiency.
TABLE-US-00013 TABLE 13 DMDS modification Volatile carbon matter SiO.sub.2 DMDS N.sub.2 Temperature (° C.) pH content at 105° C. Auxiliary (kg/h) (kg/h) (kg/h) Furnace-1 Furnace-2 Furnace-3 value (%) (%) gas II-2 30 2.1 78 120-200 150-220 200-300 5.5 1.33 0.32 HCl V-1 30 2.1 78 120-200 150-220 200-300 5.9 1.35 0.32 NH.sub.3 C-4 30 3.2 72 180-250 200-300 250-350 5 1.22 0.42 none
[0131] As shown in Table 13, the amount of C-4 modifier is 52% higher than that of the others. The amount of nitrogen is also lower, and the reaction temperature is higher, but its carbon content is over 8% lower, which indicates that both HCl and NH.sub.3 can promote the modification reaction and improve the reaction efficiency.
[0132] The technical features of the above embodiments can be combined arbitrarily. To simplify description, all possible combinations of the technical features of the above embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be the scope recorded in the description.
[0133] The above embodiments express several implementations of the present disclosure only. The description of the embodiments is relatively specific and detailed, but may not therefore be construed as the limitation on the patent scope of the present disclosure. It should be noted that a person of ordinary skill in the art may further make several variations and improvements without departing from the concept of the present disclosure. These variations and improvements all fall within the protection scope of the present disclosure. Therefore, the patent protection scope of the present disclosure shall be defined by the appended claims.