CN109279808B - Sulfonated cellulose water reducing agent based on porous carbon sulfonic acid catalyst loaded with simple substance tin and preparation method thereof - Google Patents
Sulfonated cellulose water reducing agent based on porous carbon sulfonic acid catalyst loaded with simple substance tin and preparation method thereof Download PDFInfo
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention provides a sulfonated cellulose water reducing agent based on a porous carbon sulfonic acid catalyst loaded with elemental tin and a preparation method thereof, wherein the preparation method comprises the following steps: mixing the nano silicon dioxide microspheres with a carbon source solution, heating to remove a solvent, heating to carbonize, and removing silicon to obtain a porous carbon carrier; then heating and sulfonating the porous carbon carrier to obtain a porous carbon sulfonic acid carrier; then placing the porous carbon sulfonic acid carrier in a tin dichloride solution and a ferric iron solution in sequence, wherein the retention system is acidic, reacting, spin-drying and calcining at high temperature to obtain the porous carbon sulfonic acid catalyst loaded with simple substance tin; and finally, placing dichloromethane containing activated micro-nano cellulose pulp into an intermittent reaction kettle, adding a porous carbon sulfonic acid catalyst loaded with elemental tin, performing pre-sulfonation treatment under rapid stirring and rapid temperature rise, then introducing a sulfonating agent, performing heat preservation reaction under high-speed stirring and slow temperature rise, and rapidly cooling to room temperature after the reaction is stopped to obtain the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with elemental tin.
Description
Technical Field
The invention belongs to the technical field of sulfonated water reducing agent materials, and particularly relates to a sulfonated cellulose water reducing agent based on a porous carbon sulfonic acid catalyst loaded with elemental tin and a preparation method thereof.
Background
The cellulose is a linear macromolecular formed by connecting a plurality of D-glucopyranoses by beta- (1-4) glycosidic bonds, a large number of hydroxyl groups exist on a cellulose molecular chain, the cellulose has the characteristics of easy chemical reaction, easy modification and utilization and the like, and ionic groups capable of acting with the surface of a material can be introduced to the cellulose molecular chain to prepare the sulfonated cellulose water reducing agent. The sulfonation reaction is a reaction process for introducing sulfonic groups or sulfonyl chloride groups into organic molecules, and can be divided into direct sulfonation nucleus indirect sulfonation, wherein the sulfonating agents comprise concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, chlorosulfonic acid, chlorine gas added to sulfur dioxide, oxygen added to sulfur dioxide, sodium sulfite and the like, and the sulfonation reaction is complex, and needs to undergo the processes of firstly absorbing heat, then releasing a large amount of heat, and then carrying out a stable reaction, so that the quality and the performance of a final product are greatly influenced by the control temperature in the reaction process.
Chinese patent CN1126260 discloses a sulfonated cellulose and a preparation method thereof, which comprises oxidizing cellulose fibers with sodium metaperiodate/sodium paraperiodate/periodic acid/sodium hypochlorite/hydrogen peroxide/ozone/potassium dichromate/potassium permanganate/sodium chlorite oxidizing agent at about 20-55 ℃ and about 3.0-4.6 pH to form aldehyde cellulose, washing the cellulose fibers with water, and then sulfonating the oxidized cellulose with sodium bisulfite as sulfonating agent at about 25-90 ℃ and about 3-4.5 pH to form a sulfonated cellulose having a degree of substitution of sulfo groups of about 0.01-0.1. A process for preparing high-effect water-reducing agent of bio-sulfate/sulfonate disclosed by Chinese patent CN105985043A includes such steps as mixing 1, 2-dichloroethane with the residues or natural color paste of wheat, rice, corn, potato, oil, cotton, cane and other crops, or raw plant material or natural color paste of recovered waste paper pulp, stirring at 10-25 deg.C, adding the solution of SO3 in 1, 2-dichloroethane, reacting at 20-35 deg.C for 1-6 hr, filtering to remove solvent, slowly adding solid to the alkaline water-soluble liquid, neutralizing by acid or alkali until pH is 7-9 to obtain the aqueous solution of cellulose sulfate/sulfonate with sulfonation degree of 1 and the solid of unreacted raw material, directly using the aqueous solution of cellulose sulfate/sulfonate with sulfonation degree of 1 as water-reducing agent, or the water reducer is compounded with the existing water reducers such as polycarboxylic acid series, naphthalene series and sulfonated lignin water reducers to improve the effect. According to the prior art, the sulfonated cellulose water reducing agent with different sulfonation degrees can be prepared by taking cellulose with different crystallinity degrees as a raw material and under the action of different sulfonating agents, but at present, researches on the aspect of preparing the sulfonated cellulose water reducing agent by accurately controlling the temperature are not common.
Disclosure of Invention
The invention aims to solve the technical problem of providing a sulfonated cellulose water reducing agent based on porous carbon sulfonic acid catalyst loaded with elemental tin and a preparation method thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a sulfonated cellulose water reducing agent based on a porous carbon sulfonic acid catalyst loaded with elemental tin comprises the following steps:
(1) soaking the nano silicon dioxide microspheres in a carbon source solution, uniformly stirring at room temperature, heating to remove the solvent, introducing inert gas, continuously heating for carbonization, taking out, removing silicon, grinding and drying to obtain a porous carbon carrier;
(2) adding a sulfonating agent into the porous carbon carrier prepared in the step (1), heating for sulfonation, diluting and filtering to obtain a porous carbon sulfonic acid carrier;
according to the invention, after a silicon source and a carbon source are mixed, the carbon source is permeated into the interior and the surface of the nano-silica microsphere, and the porous carbon sulfonic acid carrier with high-density sulfonic acid groups can be prepared through heating carbonization and sulfonation treatment, has a certain sulfonation effect, can replace a sulfonating agent to perform sulfonation treatment on cellulose, and is high in catalytic activity point, large in specific surface area and beneficial to improvement of the catalytic effect of the carbon sulfonic acid on cellulose sulfonation.
The method uses the mixture of sulfur trioxide and air as a sulfonating agent, so that the sulfonation reaction is mild, the control is easy, the by-products are few, and the method is favorable for improving the density of sulfonic acid groups in the carbon sulfonic acid.
(3) Placing the porous carbon sulfonic acid carrier prepared in the step (2) in a tin dichloride solution, uniformly stirring, taking out, placing in a ferric iron solution, keeping the system acidic, continuously stirring, taking out, spin-drying, and calcining at high temperature to obtain a porous carbon sulfonic acid catalyst loaded with simple substance tin;
the method utilizes the replacement reaction of ferric iron and bivalent tin to produce simple substance tin and bivalent iron, the bivalent iron is dissolved in the solution, the simple substance tin is precipitated in the interior and on the surface of the porous carbon sulfonic acid, the active point of the catalyst is further improved, the simple substance tin has certain capacity of quickly absorbing heat and slowly releasing heat, a certain effect of stabilizing the reaction temperature can be achieved, the generation of reaction byproducts is further reduced, and the sulfonation rate is improved.
(4) Adding activated micro-nano cellulose pulp into dichloromethane, uniformly dispersing, transferring to an intermittent reaction kettle, adding the porous carbon sulfonic acid catalyst loaded with elemental tin prepared in the step (3), stirring while quickly heating for pre-sulfonation treatment, then introducing a sulfonating agent, stirring while slowly heating, performing heat preservation reaction, quickly cooling to room temperature after the reaction is stopped, taking out, repeatedly washing, and performing vacuum drying to obtain the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with elemental tin.
The invention takes activated micro-nano cellulose pulp as a raw material, the micro-nano cellulose has small size and is easy to rapidly contact and react with a catalyst and a sulfonating agent, and after activation, the surface of the micro-nano cellulose contains more active groups, so that the sulfonation reaction rate is further improved.
Preferably, in the step (1), the carbon source in the carbon source solution is sucrose, glucose or starch.
Preferably, in the step (1), the mass ratio of the carbon source to the silica is 2-2.2: 1.
Preferably, in the step (1), the temperature-raising carbonization process includes: heating from 90-100 ℃ to 170-180 ℃ at the speed of 3-5 ℃/min, preserving heat for pre-carbonization for 3-4h, then heating to 420-480 ℃ at the speed of 1-2 ℃/min, preserving heat for carbonization for 2-4 h.
Preferably, in the step (1), the solvent for removing silicon is a mixture of hydrofluoric acid and nitric acid with a volume ratio of 95-98: 2-5.
Preferably, in the step (2), the sulfonating agent is a mixture of sulfur trioxide and air, the volume fraction of the sulfur trioxide is 5.2-5.6%, and the molar ratio of the sulfur trioxide to the porous carbon carrier is 1-1.03: 1.
Preferably, in the step (2), the temperature for raising the temperature and sulfonating is 35-42 ℃, and the residence time of the sulfonating agent is 0.1-0.15 s.
Preferably, in the step (3), the molar ratio of the porous carbon sulfonic acid carrier, the tin dichloride and the ferric iron is 1: 0.002-0.008: 0.01.
preferably, in the step (4), the temperature raising process includes: adding the porous carbon sulfonic acid catalyst loaded with simple substance tin prepared in the step (4), rapidly heating to 40-45 ℃ at the speed of 20-50 ℃/min under the stirring speed of 6000-8000r/min for pre-sulfonation treatment for 30-60min, then introducing a sulfonating agent, slowly heating to 50-53 ℃ at the speed of 0.3-0.5 ℃/min while stirring at the speed of 12000-15000r/min, and carrying out heat preservation reaction for 15-45min, wherein the retention time of the sulfonating agent is 0.1-0.15 s.
The invention also claims any sulfonated cellulose water reducing agent based on the porous carbon sulfonic acid catalyst loaded with the simple substance tin.
Compared with the prior art, the invention has the following beneficial effects:
the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with elemental tin, which is prepared by the invention, is prepared by taking activated micro-nano cellulose as a main raw material, taking porous carbon sulfonic acid loaded with elemental tin as a catalyst, taking sulfur trioxide and air as a sulfonating agent, and improving the catalytic activity, temperature sensitivity and adsorbability of the catalyst, reducing the intensity of sulfonation reaction and comprehensively controlling the sulfonated cellulose process by reducing the size of the raw material, thereby being beneficial to obtaining the sulfonated cellulose water reducer with high sulfonation degree and improving the service performance of the sulfonated cellulose water reducer.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1:
(1) soaking nano silicon dioxide microspheres in a sucrose solution according to the mass ratio of a carbon source to silicon dioxide of 2:1, uniformly stirring at room temperature, heating to 90 ℃ to remove a solvent, introducing an inert gas, heating to 170 ℃ at the speed of 3 ℃/min, preserving heat for pre-carbonization for 3h, heating to 420 ℃ at the speed of 1 ℃/min, preserving heat for carbonization for 2h, taking out, removing silicon by using a mixture of hydrofluoric acid and nitric acid with the volume ratio of 95:2, grinding and drying to obtain the porous carbon carrier.
(2) Adding a mixture containing 5.2% of sulfur trioxide and air into the porous carbon carrier as a sulfonating agent according to the molar ratio of the sulfur trioxide to the porous carbon carrier of 1:1, heating to 35 ℃ for sulfonation, wherein the retention time of the sulfonating agent is 0.1s, diluting and filtering to obtain the porous carbon sulfonic acid carrier.
(3) According to the molar ratio of the porous carbon sulfonic acid carrier, the tin dichloride and the ferric iron being 1: 0.002: 0.01, placing the porous carbon sulfonic acid carrier in tin dichloride solution, uniformly stirring, taking out, placing in ferric iron solution, keeping the acidity system, continuously stirring, taking out, spin-drying, and calcining at the high temperature of 450 ℃ to obtain the porous carbon sulfonic acid catalyst loaded with simple substance tin.
(4) Adding activated micro-nano cellulose pulp into dichloromethane, uniformly dispersing, transferring to an intermittent reaction kettle, adding a porous carbon sulfonic acid catalyst loaded with elemental tin, rapidly heating to 40 ℃ at a speed of 20 ℃/min under a stirring speed of 6000r/min, performing pre-sulfonation treatment for 30min, then introducing a sulfonating agent, slowly heating to 50 ℃ at a speed of 0.3 ℃/min while stirring at a speed of 12000r/min, performing heat preservation reaction for 15min, wherein the retention time of the sulfonating agent is 0.1s, rapidly cooling to room temperature after the reaction is stopped, taking out, repeatedly washing, and performing vacuum drying to obtain the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with elemental tin.
Example 2:
(1) according to the mass ratio of a carbon source to silicon dioxide of 2.2:1, soaking nano silicon dioxide microspheres in a glucose solution, uniformly stirring at room temperature, heating to 100 ℃ to remove a solvent, introducing an inert gas, heating to 180 ℃ at the speed of 5 ℃/min, preserving heat for pre-carbonization for 4h, heating to 480 ℃ at the speed of 2 ℃/min, preserving heat for carbonization for 4h, taking out, removing silicon by using a mixture of hydrofluoric acid and nitric acid at the volume ratio of 98:5, grinding and drying to obtain the porous carbon carrier.
(2) Adding a mixture containing 5.6% of sulfur trioxide and air into the porous carbon carrier as a sulfonating agent according to the molar ratio of the sulfur trioxide to the porous carbon carrier of 1.03:1, heating to 42 ℃ for sulfonation, wherein the retention time of the sulfonating agent is 0.15s, diluting and filtering to obtain the porous carbon sulfonic acid carrier.
(3) According to the molar ratio of the porous carbon sulfonic acid carrier, the tin dichloride and the ferric iron being 1: 0.008: 0.01, placing the porous carbon sulfonic acid carrier in tin dichloride solution, uniformly stirring, taking out, placing in ferric iron solution, keeping the acidity system, continuously stirring, taking out, spin-drying, and calcining at the high temperature of 500 ℃ to obtain the porous carbon sulfonic acid catalyst loaded with simple substance tin.
(4) Adding activated micro-nano cellulose pulp into dichloromethane, uniformly dispersing, transferring to an intermittent reaction kettle, adding a porous carbon sulfonic acid catalyst loaded with elemental tin, rapidly heating to 45 ℃ at the speed of 50 ℃/min under the stirring speed of 8000r/min, performing pre-sulfonation treatment for 60min, then introducing a sulfonating agent, slowly heating to 53 ℃ at the speed of 0.5 ℃/min while stirring at the speed of 15000r/min, performing heat preservation reaction for 45min, wherein the retention time of the sulfonating agent is 0.15s, rapidly cooling to room temperature after the reaction is stopped, taking out, repeatedly washing, and performing vacuum drying to obtain the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with elemental tin.
Example 3:
(1) according to the mass ratio of a carbon source to silicon dioxide of 2.1:1, soaking nano silicon dioxide microspheres in a sucrose, glucose and starch solution, stirring uniformly at room temperature, heating to 95 ℃ to remove a solvent, introducing an inert gas, heating to 175 ℃ at the speed of 3.5 ℃/min, preserving heat, pre-carbonizing for 3.5h, heating to 450 ℃ at the speed of 1.3 ℃/min, preserving heat, carbonizing for 2h, taking out, removing silicon by using a mixture of hydrofluoric acid and nitric acid at the volume ratio of 96:3, grinding and drying to obtain the porous carbon carrier.
(2) Adding a mixture containing 5.5% of sulfur trioxide and air into the porous carbon carrier as a sulfonating agent according to the molar ratio of the sulfur trioxide to the porous carbon carrier of 1.01:1, heating to 38 ℃ for sulfonation, wherein the retention time of the sulfonating agent is 0.13s, diluting and filtering to obtain the porous carbon sulfonic acid carrier.
(3) According to the molar ratio of the porous carbon sulfonic acid carrier, the tin dichloride and the ferric iron being 1: 0.005: 0.01, placing the porous carbon sulfonic acid carrier in a tin dichloride solution, uniformly stirring, taking out, placing in a ferric iron solution, keeping the acidity of the system, continuously stirring, taking out, spin-drying, and calcining at 490 ℃ to obtain the porous carbon sulfonic acid catalyst loaded with simple substance tin.
(4) Adding activated micro-nano cellulose pulp into dichloromethane, uniformly dispersing, transferring to an intermittent reaction kettle, adding a porous carbon sulfonic acid catalyst loaded with elemental tin, rapidly heating to 42 ℃ at a speed of 35 ℃/min under a stirring speed of 7000r/min for pre-sulfonation for 45min, then introducing a sulfonating agent, slowly heating to 51 ℃ at a speed of 0.35 ℃/min while stirring at a speed of 14000r/min, carrying out heat preservation reaction for 25min, wherein the retention time of the sulfonating agent is 0.13s, rapidly cooling to room temperature after the reaction is stopped, taking out, repeatedly washing, and carrying out vacuum drying to obtain the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with elemental tin.
Example 4:
(1) according to the mass ratio of a carbon source to silicon dioxide of 2.1:1, soaking nano silicon dioxide microspheres in a sucrose, glucose and starch solution, stirring uniformly at room temperature, heating to 98 ℃ to remove a solvent, introducing an inert gas, heating to 173 ℃ at the speed of 4.5 ℃/min, preserving heat, pre-carbonizing for 3.5h, heating to 460 ℃ at the speed of 1.5 ℃/min, preserving heat, carbonizing for 2.5h, taking out, removing silicon by using a mixture of hydrofluoric acid and nitric acid at the volume ratio of 97:3.5, grinding and drying to obtain the porous carbon carrier.
(2) Adding a mixture containing 5.3% of sulfur trioxide and air into the porous carbon carrier as a sulfonating agent according to the molar ratio of the sulfur trioxide to the porous carbon carrier of 1.02:1, heating to 39 ℃ for sulfonation, wherein the retention time of the sulfonating agent is 0.13s, diluting and filtering to obtain the porous carbon sulfonic acid carrier.
(3) According to the molar ratio of the porous carbon sulfonic acid carrier, the tin dichloride and the ferric iron being 1: 0.007: 0.01, placing the porous carbon sulfonic acid carrier in a tin dichloride solution, uniformly stirring, taking out, placing in a ferric iron solution, keeping the acidity of the system, continuously stirring, taking out, spin-drying, and calcining at 490 ℃ to obtain the porous carbon sulfonic acid catalyst loaded with simple substance tin.
(4) Adding activated micro-nano cellulose pulp into dichloromethane, uniformly dispersing, transferring to an intermittent reaction kettle, adding a porous carbon sulfonic acid catalyst loaded with elemental tin, rapidly heating to 42 ℃ at a speed of 45 ℃/min under a stirring speed of 7500r/min, performing pre-sulfonation treatment for 50min, then introducing a sulfonating agent, slowly heating to 51 ℃ at a speed of 0.45 ℃/min while stirring at a speed of 14000r/min, performing heat preservation reaction for 30min, wherein the retention time of the sulfonating agent is 0.1-0.15s, rapidly cooling to room temperature after the reaction is stopped, taking out, repeatedly washing, and performing vacuum drying to obtain the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with elemental tin.
Example 5:
(1) according to the mass ratio of a carbon source to silicon dioxide of 2:1, soaking nano silicon dioxide microspheres in a sucrose, glucose and starch solution, stirring uniformly at room temperature, heating to 100 ℃ to remove a solvent, introducing an inert gas, heating to 180 ℃ at the speed of 3 ℃/min, preserving heat for pre-carbonization for 3h, heating to 420 ℃ at the speed of 2 ℃/min, preserving heat for carbonization for 4h, taking out, removing silicon by using a mixture of hydrofluoric acid and nitric acid at the volume ratio of 95:5, grinding and drying to obtain the porous carbon carrier.
(2) Adding a mixture containing 5.6% of sulfur trioxide and air into the porous carbon carrier as a sulfonating agent according to the molar ratio of the sulfur trioxide to the porous carbon carrier of 1:1, heating to 35 ℃ for sulfonation, wherein the retention time of the sulfonating agent is 0.15s, diluting and filtering to obtain the porous carbon sulfonic acid carrier.
(3) According to the molar ratio of the porous carbon sulfonic acid carrier, the tin dichloride and the ferric iron being 1: 0.002: 0.01, placing the porous carbon sulfonic acid carrier in tin dichloride solution, uniformly stirring, taking out, placing in ferric iron solution, keeping the acidity system, continuously stirring, taking out, spin-drying, and calcining at the high temperature of 500 ℃ to obtain the porous carbon sulfonic acid catalyst loaded with simple substance tin.
(4) Adding activated micro-nano cellulose pulp into dichloromethane, uniformly dispersing, transferring to an intermittent reaction kettle, adding a porous carbon sulfonic acid catalyst loaded with elemental tin, rapidly heating to 40 ℃ at a speed of 50 ℃/min under a stirring speed of 6000r/min, performing pre-sulfonation treatment for 60min, then introducing a sulfonating agent, slowly heating to 50 ℃ at a speed of 0.5 ℃/min while stirring at a speed of 12000r/min, performing heat preservation reaction for 45min, wherein the retention time of the sulfonating agent is 0.1s, rapidly cooling to room temperature after the reaction is stopped, taking out, repeatedly washing, and performing vacuum drying to obtain the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with elemental tin.
Example 6:
(1) according to the mass ratio of a carbon source to silicon dioxide of 2.2:1, soaking nano silicon dioxide microspheres in a sucrose, glucose and starch solution, stirring uniformly at room temperature, heating to 90 ℃ to remove a solvent, introducing an inert gas, heating to 170 ℃ at the speed of 5 ℃/min, preserving heat for pre-carbonization for 4h, heating to 480 ℃ at the speed of 1 ℃/min, preserving heat for carbonization for 2h, taking out, removing silicon by using a mixture of hydrofluoric acid and nitric acid at the volume ratio of 98:2, grinding and drying to obtain the porous carbon carrier.
(2) Adding a mixture containing 5.2% of sulfur trioxide and air into the porous carbon carrier as a sulfonating agent according to the molar ratio of the sulfur trioxide to the porous carbon carrier of 1.03:1, heating to 42 ℃ for sulfonation, wherein the retention time of the sulfonating agent is 0.1s, diluting and filtering to obtain the porous carbon sulfonic acid carrier.
(3) According to the molar ratio of the porous carbon sulfonic acid carrier, the tin dichloride and the ferric iron being 1: 0.008: 0.01, placing the porous carbon sulfonic acid carrier in tin dichloride solution, uniformly stirring, taking out, placing in ferric iron solution, keeping the acidity system, continuously stirring, taking out, spin-drying, and calcining at the high temperature of 450 ℃ to obtain the porous carbon sulfonic acid catalyst loaded with simple substance tin.
(4) Adding activated micro-nano cellulose pulp into dichloromethane, uniformly dispersing, transferring to an intermittent reaction kettle, adding a porous carbon sulfonic acid catalyst loaded with elemental tin, rapidly heating to 45 ℃ at the speed of 20 ℃/min under the stirring speed of 8000r/min, carrying out pre-sulfonation treatment for 30min, then introducing a sulfonating agent, slowly heating to 53 ℃ at the speed of 0.3 ℃/min while stirring at the speed of 15000r/min, carrying out heat preservation reaction for 15min, wherein the retention time of the sulfonating agent is 0.15s, rapidly cooling to room temperature after the reaction is stopped, taking out, repeatedly washing, and carrying out vacuum drying to obtain the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with elemental tin.
The results of the detection on the total acid amount, the sulfonic acid amount and the sulfonation degree of the sulfonated cellulose water reducing agent based on the porous carbon sulfonic acid catalyst loaded with the elemental tin prepared in the examples 1 to 6 are as follows:
as can be seen from the above table, the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with elemental tin prepared by the invention contains abundant sulfonic acid groups, so that the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with elemental tin has strong hydrophilicity, good dispersibility and water-reducing property, and certain temperature resistance and salt resistance.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A preparation method of a sulfonated cellulose water reducing agent based on a porous carbon sulfonic acid catalyst loaded with elemental tin is characterized by comprising the following steps:
(1) soaking the nano silicon dioxide microspheres in a carbon source solution, uniformly stirring at room temperature, heating to remove the solvent, introducing inert gas, continuously heating for carbonization, taking out, removing silicon, grinding and drying to obtain a porous carbon carrier;
(2) adding a sulfonating agent into the porous carbon carrier prepared in the step (1), heating for sulfonation, diluting and filtering to obtain a porous carbon sulfonic acid carrier;
(3) placing the porous carbon sulfonic acid carrier prepared in the step (2) in a tin dichloride solution, uniformly stirring, taking out, placing in a ferric iron solution, keeping the system acidic, continuously stirring, taking out, spin-drying, and calcining at high temperature to obtain a porous carbon sulfonic acid catalyst loaded with simple substance tin;
(4) adding activated micro-nano cellulose pulp into dichloromethane, uniformly dispersing, transferring to an intermittent reaction kettle, adding the porous carbon sulfonic acid catalyst loaded with elemental tin prepared in the step (3), stirring while quickly heating for pre-sulfonation treatment, then introducing a sulfonating agent, stirring while slowly heating, performing heat preservation reaction, quickly cooling to room temperature after the reaction is stopped, taking out, repeatedly washing, and performing vacuum drying to obtain the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with elemental tin.
2. The preparation method of the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with the elemental tin according to claim 1 is characterized by comprising the following steps: in the step (1), the carbon source in the carbon source solution is sucrose, glucose and starch.
3. The preparation method of the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with the elemental tin according to claim 1 is characterized by comprising the following steps: in the step (1), the mass ratio of the carbon source to the silicon dioxide is 2-2.2: 1.
4. The preparation method of the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with the elemental tin according to claim 1 is characterized by comprising the following steps: in the step (1), the temperature-rising carbonization process comprises the following steps: heating from 90-100 ℃ to 170-180 ℃ at the speed of 3-5 ℃/min, preserving heat for pre-carbonization for 3-4h, then heating to 420-480 ℃ at the speed of 1-2 ℃/min, preserving heat for carbonization for 2-4 h.
5. The preparation method of the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with the elemental tin according to claim 1 is characterized by comprising the following steps: in the step (1), the solvent for removing silicon is a mixture of hydrofluoric acid and nitric acid with a volume ratio of 95-98: 2-5.
6. The preparation method of the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with the elemental tin according to claim 1 is characterized by comprising the following steps: in the step (2), the sulfonating agent is a mixture of sulfur trioxide and air, the volume fraction of the sulfur trioxide is 5.2-5.6%, and the molar ratio of the sulfur trioxide to the porous carbon carrier is 1-1.03: 1.
7. The preparation method of the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with the elemental tin according to claim 1 is characterized by comprising the following steps: in the step (2), the temperature for heating and sulfonating is 35-42 ℃, and the residence time of the sulfonating agent is 0.1-0.15 s.
8. The preparation method of the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with the elemental tin according to claim 1 is characterized by comprising the following steps: in the step (3), the molar ratio of the porous carbon sulfonic acid carrier to the tin dichloride to the ferric iron is 1: 0.002-0.008: 0.01.
9. the preparation method of the sulfonated cellulose water reducer based on the porous carbon sulfonic acid catalyst loaded with the elemental tin according to claim 1 is characterized by comprising the following steps: in the step (4), the temperature raising process comprises the following steps: adding the porous carbon sulfonic acid catalyst loaded with simple substance tin prepared in the step (4), rapidly heating to 40-45 ℃ at the speed of 20-50 ℃/min under the stirring speed of 6000-8000r/min for pre-sulfonation treatment for 30-60min, then introducing a sulfonating agent, slowly heating to 50-53 ℃ at the speed of 0.3-0.5 ℃/min while stirring at the speed of 12000-15000r/min, and carrying out heat preservation reaction for 15-45min, wherein the retention time of the sulfonating agent is 0.1-0.15 s.
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| JPH01301595A (en) * | 1988-05-31 | 1989-12-05 | Mitsubishi Gas Chem Co Inc | Production of silicon nitride whisker |
| CN101455975A (en) * | 2007-12-14 | 2009-06-17 | 北京化工大学 | Porous carbon nanometer fiber-supported nanocrystal catalyst and preparation method thereof |
| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
| CN106582716A (en) * | 2016-12-08 | 2017-04-26 | 陕西品达石化有限公司 | Preparation method of biological carbon sulfonic acid |
| CN107408677A (en) * | 2015-03-31 | 2017-11-28 | 株式会社Lg 化学 | Porous silicon Si oxide carbon complex and its preparation method |
| CN108091841A (en) * | 2017-12-05 | 2018-05-29 | 陕西科技大学 | A kind of method for preparing porous carbon load tin dioxide composite material |
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| JPH01301595A (en) * | 1988-05-31 | 1989-12-05 | Mitsubishi Gas Chem Co Inc | Production of silicon nitride whisker |
| CN101455975A (en) * | 2007-12-14 | 2009-06-17 | 北京化工大学 | Porous carbon nanometer fiber-supported nanocrystal catalyst and preparation method thereof |
| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
| CN107408677A (en) * | 2015-03-31 | 2017-11-28 | 株式会社Lg 化学 | Porous silicon Si oxide carbon complex and its preparation method |
| CN106582716A (en) * | 2016-12-08 | 2017-04-26 | 陕西品达石化有限公司 | Preparation method of biological carbon sulfonic acid |
| CN108091841A (en) * | 2017-12-05 | 2018-05-29 | 陕西科技大学 | A kind of method for preparing porous carbon load tin dioxide composite material |
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