CN109279808A - A kind of sulfonated cellulose water-reducing agent of porous carbon sulfonic acid catalyst and preparation method thereof based on load simple substance tin - Google Patents
A kind of sulfonated cellulose water-reducing agent of porous carbon sulfonic acid catalyst and preparation method thereof based on load simple substance tin Download PDFInfo
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- CN109279808A CN109279808A CN201811158858.5A CN201811158858A CN109279808A CN 109279808 A CN109279808 A CN 109279808A CN 201811158858 A CN201811158858 A CN 201811158858A CN 109279808 A CN109279808 A CN 109279808A
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- C—CHEMISTRY; METALLURGY
- 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
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- C—CHEMISTRY; METALLURGY
- 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
- 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 present invention provides a kind of sulfonated cellulose water-reducing agent of porous carbon sulfonic acid catalyst and preparation method thereof based on load simple substance tin, the following steps are included: nano silica microsphere is mixed with carbon source solution, heating removal solvent, heating carbonization, except silicon, porous carbon support is obtained；Then porous carbon support is handled to obtain porous carbon sulfonic acid carrier through heating sulfonation；Porous carbon sulfonic acid carrier is first placed in stannous chloride solution and trivalent ferrous solution again, keeping system is acidity, and reaction is spin-dried for, high-temperature calcination, obtains the porous carbon sulfonic acid catalyst of load simple substance tin；Finally the methylene chloride of the micro-nano cellulose slurry containing activation is placed in batch reactor, the porous carbon sulfonic acid catalyst of load simple substance tin is added, in lower pre- sulfonation processing of quickly stirring and be rapidly heated, then pass to sulfonating agent, the insulation reaction under high-speed stirred and slowly heating, reaction is rapidly decreased to room temperature after stopping, and obtains the sulfonated cellulose water-reducing agent of the porous carbon sulfonic acid catalyst based on load simple substance tin.
Description
Technical field
The invention belongs to sulfonated water reducing agent field of material technology, and in particular to a kind of porous carbon sulphur based on load simple substance tin
Sulfonated cellulose water-reducing agent of acid catalyst and preparation method thereof.
Background technique
Cellulose is the linear macromolecules being formed by connecting each other with β-(1-4) glycosidic bond by many D- glucopyranoses, fiber
There are a large amount of hydroxyl on plain strand, have be prone to chemical reaction, it is easily modified the characteristics such as utilize, can will be with material
The ionic group of surface action is introduced on cellulose molecular chain, and sulfonated cellulose water-reducing agent is prepared.Sulfonating reaction is one
Introduce the reaction process of sulfonic group or sulfuryl chlorio kind into organic molecule, sulfonating reaction can be divided into that Direct Sulfonation is internuclear to connect sulphur
Change, wherein sulfonating agent has the concentrated sulfuric acid, oleum, sulfur trioxide, chlorosulfonic acid, sulfur dioxide chlorination gas, sulfur dioxide oxygen
With sodium sulfite etc., and sulfonating reaction is complex, need to undergo and first absorb heat, then highly exothermic again, smooth reaction later
Process, therefore respectively control temperature in reaction process and all have a great impact to the quality of final products and performance.
Sulfonated cellulose disclosed in Chinese patent CN1126260 and preparation method thereof, in about 20 DEG C -55 DEG C and about 3.0-
Under 4.6 pH value, with sodium metaperiodate/sodium paraperiodate/periodic acid/sodium hypochlorite/hydrogen peroxide/ozone/potassium bichromate/height
The oxidizing cellulose fibre of potassium manganate/sodium chlorite forms aldocellulose, cellulose fibre is washed with water, then uses
Sodium hydrogensulfite is as sulfonating agent, and under about 25 DEG C -90 DEG C and about 3-4.5 of pH value, the cellulose of the sulfonation oxidation forms sulphur
Base degree of substitution is the sulfonated cellulose of about 0.01-0.1.The sulfuric ester of biology base disclosed in Chinese patent CN105985043A/sulfonic acid
Salt is as high efficiency water reducing agent production new technique, with wheat, rice, corn, potato, oil plant, cotton, sugarcane and other crops
Stalk or wood machining residues or natural color pulp or reclaimed waste paper slurry plant roughing raw material or natural color pulp are as raw material, and 1,2-
It in dichloroethanes, is stirred at 10-25 DEG C, 1, the 2- dichloroethane solution dissolved with SO3 is added, it is small that 1-6 is reacted at 20-35 DEG C
Shi Hou is filtered to remove solvent, and solid is slowly added in the alkali water-soluble liquid of sub-cooled, and progress acid-base neutralization to pH is 7-
9, the cellulose sulfuric acid ester/sulfonic acid saline solution and unresponsive raw material solid of sulfonation degree 1 or so, the sulfonation degree 1 can be obtained
Cellulose sulfuric acid ester/sulfonic acid saline solution of left and right can be directly used as water-reducing agent, or with existing water-reducing agent such as polycarboxylic-acid, naphthalene
System, lignosulfonate water-reducing agent compounding promote effect.By the above-mentioned prior art it is found that using the cellulose of different crystallinity as original
The sulfonated cellulose water-reducing agent of different sulfonation degrees can be prepared in material, the effect through different sulfonating agents, but at present for essence
Research in terms of true temperature control prepares sulfonated cellulose water-reducing agent is actually rare.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of sulphurs of porous carbon sulfonic acid catalyst based on load simple substance tin
Cellulose water-reducing agent and preparation method thereof, the present invention is using the porous carbon sulfonic acid of the sulfonated reaction preparation of porous carbon materials as load
Body, surface deposit simple substance tin, not only increase the catalytic activity of catalyst, also make catalyst that there is certain phase transformation and sulfonation to make
With, be conducive to keep cellulose sulfonic acid process temperature stability, and with batch reactor synergy, improve sulfonated cellulose
Sulphonation rate, then improve water-reducing agent performance.
In order to solve the above technical problems, the technical scheme is that
A kind of preparation method of the sulfonated cellulose water-reducing agent of the porous carbon sulfonic acid catalyst based on load simple substance tin, including
Following steps:
(1) nano silica microsphere is impregnated in carbon source solution, after being stirred at room temperature uniformly, heating removal is molten
Agent is passed through inert gas, continues heating carbonization, takes out, remove silicon, mill-drying obtains porous carbon support；
(2) sulfonating agent is added in the porous carbon support by step (1) preparation, and heat up sulfonation, and dilute filtration obtains porous
Carbon sulfonic acid carrier；
After the present invention mixes silicon source and carbon source, carbon source is infiltrated through to the inside and surface of nano silica microsphere, is passed through
Heating carbonization and sulfonation processing, can be prepared the porous carbon sulfonic acid carrier of high density sulfonic acid group, the porous carbon sulfonic acid carrier
With certain sulfonation, sulfonating agent can be replaced to carry out sulfonation processing to cellulose, and the porous carbon sulfonic acid carrier is urged
It is high to change active site, large specific surface area is conducive to improve catalytic action of the carbon sulfonic acid to cellulose sulfonation.
The present invention first uses the mixture of sulfur trioxide and air as sulfonating agent, and sulfonating reaction is mild, is easy to control, by-product
Object is few, is conducive to the density for improving sulfonic acid group in carbon sulfonic acid.
(3) porous carbon sulfonic acid carrier prepared by step (2) is placed in stannous chloride solution, after mixing evenly, takes out, set
In trivalent ferrous solution, keeping system is acidity, continues to stir, and takes out, is spin-dried for, high-temperature calcination, obtains the more of load simple substance tin
Hole carbon sulfonic acid catalyst；
The present invention is reacted using ferric iron with stannous displacement, produces simple substance tin and ferrous iron, ferrous iron are dissolved in solution
In, simple substance tin is deposited in the inside and surface of porous carbon sulfonic acid, further increases the active site of catalyst, and simple substance tin has
The gentle slow exothermic ability of certain fast endothermic, can play the role of certain stabilization reaction temperature, further decrease anti-
The generation of by-product is answered, sulphonation rate is improved.
(4) the micro-nano cellulose slurry of activation is added in methylene chloride, is uniformly dispersed, is transferred in batch reactor,
The porous carbon sulfonic acid catalyst of the load simple substance tin of step (3) preparation is added, is rapidly heated while stirring and carries out pre- sulfonation
Processing, then passes to sulfonating agent, the heating of Huan Maning while stirring, insulation reaction, and reaction is rapidly decreased to room temperature after stopping, and takes
Out, it washs, is dried in vacuo repeatedly, obtain the sulfonated cellulose water-reducing agent of the porous carbon sulfonic acid catalyst based on load simple substance tin.
The present invention is starched using the micro-nano cellulose activated as raw material, and the size of micro-nano cellulose is small, is easy and is catalyzed
Agent and sulfonating agent Rapid contact reaction, and it is activated after, more active groups are contained on the surface of micro-nano cellulose, into one
Step improves sulfonating reaction rate, and the present invention reduces the distribution of sulfonation degree, overcome the generation of side reaction, first use by being rapidly heated
Catalyst carries out presulfiding reaction to micro-nano cellulose, is then passed through sulfonating agent again, carries out abundant sulfonating reaction, realizes liter
Temperature heat absorption and the exothermic smooth transition of sulfonation, and the porous performance of catalyst and the performance of material itself are also beneficial to control instead
The precision answered improves production efficiency.
As a preferred embodiment of the above technical solution, in the step (1), carbon source is sucrose, glucose and shallow lake in carbon source solution
Powder.
As a preferred embodiment of the above technical solution, in the step (1), the mass ratio of carbon source and silica is 2-2.2:1.
As a preferred embodiment of the above technical solution, in the step (1), the technique for the carbonization that heats up are as follows: at from 90-100 DEG C, with
The rate of 3-5 DEG C/min is warming up to 170-180 DEG C, keeps the temperature pre- charing 3-4h, is then warming up to 420- with the rate of 1-2 DEG C/min
480 DEG C, heat preservation charing 2-4h.
It as a preferred embodiment of the above technical solution, is 95-98:2-5's except the solvent of silicon is volume ratio in the step (1)
The mixture of hydrofluoric acid and nitric acid.
As a preferred embodiment of the above technical solution, in the step (2), sulfonating agent is the mixture of sulfur trioxide and air,
The volume fraction of sulfur trioxide is 5.2-5.6%, and the molar ratio of sulfur trioxide and porous carbon support is 1-1.03:1.
As a preferred embodiment of the above technical solution, in the step (2), the temperature for the sulfonation that heats up is 35-42 DEG C, sulfonating agent
Residence time is 0.1-0.15s.
As a preferred embodiment of the above technical solution, in the step (3), porous carbon sulfonic acid carrier, stannous chloride and ferric iron
Molar ratio is 1:0.002-0.008:0.01.
As a preferred embodiment of the above technical solution, in the step (4), the technique of heating are as follows: the negative of step (4) preparation is added
The porous carbon sulfonic acid catalyst of simple substance tin is carried, it is fast with the rate of 20-50 DEG C/min under the stirring rate of 6000-8000r/min
Speed is warming up to 40-45 DEG C and carries out pre- sulfonation processing 30-60min, sulfonating agent is then passed to, on one side with 12000-15000r/min's
Rate stirring is to slowly warm up to 50-53 DEG C, insulation reaction 15-45min on one side with the rate of 0.3-0.5 DEG C/min, wherein sulfonation
The residence time of agent is 0.1-0.15s.
The sulfonation of any one porous carbon sulfonic acid catalyst based on load simple substance tin is also claimed in the present invention
Cellulose water-reducing agent.
Compared with prior art, the invention has the following advantages:
It is prepared by the present invention based on load simple substance tin porous carbon sulfonic acid catalyst sulfonated cellulose water-reducing agent it is main
Raw material is activation micro-nano cellulose, and catalyst is the porous carbon sulfonic acid for loading simple substance tin, and sulfonating agent is sulfur trioxide and air
Mixture improve catalytic activity, moisture sensitivity and the adsorptivity of catalyst by reducing the size of raw material, reduce sulfonation
The severe degree of reaction, comprehensively control sulfonated cellulose technique are conducive to the sulfonated cellulose water-reducing agent for obtaining highly sulfonated, mention
The service performance of high sulfonated cellulose water-reducing agent.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1:
(1) it is 2:1 according to the mass ratio of carbon source and silica, nano silica microsphere is impregnated in sucrose solution
In, after being stirred at room temperature uniformly, 90 DEG C of removal solvents are warming up to, inert gas is passed through, is warming up to the rate of 3 DEG C/min
170 DEG C, pre- charing 3h is kept the temperature, is then warming up to 420 DEG C with the rate of 1 DEG C/min, heat preservation charing 2h takes out, is with volume ratio
The hydrofluoric acid of 95:2 and the mixture of nitric acid remove silicon, and mill-drying obtains porous carbon support.
(2) it is 1:1 according to the molar ratio of sulfur trioxide and porous carbon support, porous carbon support is added three containing 5.2%
The mixture of sulfur oxide and air is warming up to 35 DEG C of sulfonation as sulfonating agent, and the residence time of sulfonating agent is 0.1s, is diluted
Filter, obtains porous carbon sulfonic acid carrier.
It (3) is 1:0.002:0.01 according to porous carbon sulfonic acid carrier, stannous chloride and ferric iron molar ratio, by porous carbon sulphur
Acid vectors are placed in stannous chloride solution, after mixing evenly, are taken out, are placed in trivalent ferrous solution, and keeping system is acidity, are continued
Stirring is taken out, is spin-dried for, the high-temperature calcination at 450 DEG C, and the porous carbon sulfonic acid catalyst of load simple substance tin is obtained.
(4) the micro-nano cellulose slurry of activation is added in methylene chloride, is uniformly dispersed, is transferred in batch reactor,
The porous carbon sulfonic acid catalyst of load simple substance tin is added, it is fast with the rate of 20 DEG C/min under the stirring rate of 6000r/min
Speed is warming up to 40 DEG C and carries out pre- sulfonation processing 30min, then passes to sulfonating agent. while being stirred with the rate of 12000r/min
50 DEG C, insulation reaction 15min are to slowly warm up to the rate of 0.3 DEG C/min, wherein the residence time of sulfonating agent is 0.1s, reaction
It is rapidly decreased to room temperature after stopping, taking out, washs repeatedly, is dried in vacuo, obtains the porous carbon sulfonic acid catalysis based on load simple substance tin
The sulfonated cellulose water-reducing agent of agent.
Embodiment 2:
(1) it is 2.2:1 according to the mass ratio of carbon source and silica, it is molten that nano silica microsphere is impregnated in glucose
In liquid, after being stirred at room temperature uniformly, 100 DEG C of removal solvents are warming up to, inert gas is passed through, heated up with the rate of 5 DEG C/min
To 180 DEG C, pre- charing 4h is kept the temperature, is then warming up to 480 DEG C with the rate of 2 DEG C/min, heat preservation charing 4h takes out, uses volume ratio
Silicon is removed for the hydrofluoric acid of 98:5 and the mixture of nitric acid, mill-drying obtains porous carbon support.
(2) it is 1.03:1 according to the molar ratio of sulfur trioxide and porous carbon support, porous carbon support is added containing 5.6%
The mixture of sulfur trioxide and air is warming up to 42 DEG C of sulfonation as sulfonating agent, and the residence time of sulfonating agent is 0.15s, dilution
Filtering, obtains porous carbon sulfonic acid carrier.
It (3) is 1:0.008:0.01 according to porous carbon sulfonic acid carrier, stannous chloride and ferric iron molar ratio, by porous carbon sulphur
Acid vectors are placed in stannous chloride solution, after mixing evenly, are taken out, are placed in trivalent ferrous solution, and keeping system is acidity, are continued
Stirring is taken out, is spin-dried for, the high-temperature calcination at 500 DEG C, and the porous carbon sulfonic acid catalyst of load simple substance tin is obtained.
(4) the micro-nano cellulose slurry of activation is added in methylene chloride, is uniformly dispersed, is transferred in batch reactor,
The porous carbon sulfonic acid catalyst of load simple substance tin is added, it is quick with the rate of 50 DEG C/min under the stirring rate of 8000r/min
It is warming up to 45 DEG C and carries out pre- sulfonation processing 60min, then pass to sulfonating agent, with while being stirred with the rate of 15000r/min
The rate of 0.5 DEG C/min is to slowly warm up to 53 DEG C, insulation reaction 45min, and wherein the residence time of sulfonating agent is 0.15s, reaction
It is rapidly decreased to room temperature after stopping, taking out, washs repeatedly, is dried in vacuo, obtains the porous carbon sulfonic acid catalysis based on load simple substance tin
The sulfonated cellulose water-reducing agent of agent.
Embodiment 3:
(1) it is 2.1:1 according to the mass ratio of carbon source and silica, nano silica microsphere is impregnated in sucrose, Portugal
In grape sugar and starch solution, be stirred at room temperature uniformly after, be warming up to 95 DEG C of removal solvents, be passed through inert gas, with 3.5 DEG C/
The rate of min is warming up to 175 DEG C, keeps the temperature pre- charing 3.5h, is then warming up to 450 DEG C with the rate of 1.3 DEG C/min, heat preservation charing
2h takes out, and the mixture of the hydrofluoric acid and nitric acid that are 96:3 with volume ratio removes silicon, and mill-drying obtains porous carbon support.
(2) it is 1.01:1 according to the molar ratio of sulfur trioxide and porous carbon support, porous carbon support is added containing 5.5%
The mixture of sulfur trioxide and air is warming up to 38 DEG C of sulfonation as sulfonating agent, and the residence time of sulfonating agent is 0.13s, dilution
Filtering, obtains porous carbon sulfonic acid carrier.
It (3) is 1:0.005:0.01 according to porous carbon sulfonic acid carrier, stannous chloride and ferric iron molar ratio, by porous carbon sulphur
Acid vectors are placed in stannous chloride solution, after mixing evenly, are taken out, are placed in trivalent ferrous solution, and keeping system is acidity, are continued
Stirring is taken out, is spin-dried for, the high-temperature calcination at 490 DEG C, and the porous carbon sulfonic acid catalyst of load simple substance tin is obtained.
(4) the micro-nano cellulose slurry of activation is added in methylene chloride, is uniformly dispersed, is transferred in batch reactor,
The porous carbon sulfonic acid catalyst of load simple substance tin is added, it is fast with the rate of 35 DEG C/min under the stirring rate of 7000r/min
Speed is warming up to 42 DEG C and carries out pre- sulfonation processing 45min, then passes to sulfonating agent. while being stirred with the rate of 14000r/min
51 DEG C, insulation reaction 25min are to slowly warm up to the rate of 0.35 DEG C/min, wherein the residence time of sulfonating agent is 0.13s, instead
It is rapidly decreased to room temperature after should stopping, taking out, washs repeatedly, is dried in vacuo, obtains urging based on the porous carbon sulfonic acid of load simple substance tin
The sulfonated cellulose water-reducing agent of agent.
Embodiment 4:
(1) it is 2.1:1 according to the mass ratio of carbon source and silica, nano silica microsphere is impregnated in sucrose, Portugal
In grape sugar and starch solution, be stirred at room temperature uniformly after, be warming up to 98 DEG C of removal solvents, be passed through inert gas, with 4.5 DEG C/
The rate of min is warming up to 173 DEG C, keeps the temperature pre- charing 3.5h, is then warming up to 460 DEG C with the rate of 1.5 DEG C/min, heat preservation charing
2.5h takes out, and the mixture of the hydrofluoric acid and nitric acid that are 97:3.5 with volume ratio removes silicon, and mill-drying obtains porous carbon support.
(2) it is 1.02:1 according to the molar ratio of sulfur trioxide and porous carbon support, porous carbon support is added containing 5.3%
The mixture of sulfur trioxide and air is warming up to 39 DEG C of sulfonation as sulfonating agent, and the residence time of sulfonating agent is 0.13s, dilution
Filtering, obtains porous carbon sulfonic acid carrier.
It (3) is 1:0.007:0.01 according to porous carbon sulfonic acid carrier, stannous chloride and ferric iron molar ratio, by porous carbon sulphur
Acid vectors are placed in stannous chloride solution, after mixing evenly, are taken out, are placed in trivalent ferrous solution, and keeping system is acidity, are continued
Stirring is taken out, is spin-dried for, the high-temperature calcination at 490 DEG C, and the porous carbon sulfonic acid catalyst of load simple substance tin is obtained.
(4) the micro-nano cellulose slurry of activation is added in methylene chloride, is uniformly dispersed, is transferred in batch reactor,
The porous carbon sulfonic acid catalyst of load simple substance tin is added, it is fast with the rate of 45 DEG C/min under the stirring rate of 7500r/min
Speed is warming up to 42 DEG C and carries out pre- sulfonation processing 50min, then passes to sulfonating agent. while being stirred with the rate of 14000r/min
51 DEG C, insulation reaction 30min are to slowly warm up to the rate of 0.45 DEG C/min, wherein the residence time of sulfonating agent is 0.1-
0.15s, reaction are rapidly decreased to room temperature after stopping, and take out, wash repeatedly, are dried in vacuo, and obtain based on the porous of load simple substance tin
The sulfonated cellulose water-reducing agent of carbon sulfonic acid catalyst.
Embodiment 5:
(1) it is 2:1 according to the mass ratio of carbon source and silica, nano silica microsphere is impregnated in sucrose, grape
In sugar and starch solution, after being stirred at room temperature uniformly, 100 DEG C of removal solvents is warming up to, inert gas are passed through, with 3 DEG C/min
Rate be warming up to 180 DEG C, keep the temperature pre- charing 3h, be then warming up to 420 DEG C with the rate of 2 DEG C/min, heat preservation charing 4h takes
Out, the mixture of the hydrofluoric acid and nitric acid that are 95:5 with volume ratio removes silicon, and mill-drying obtains porous carbon support.
(2) it is 1:1 according to the molar ratio of sulfur trioxide and porous carbon support, porous carbon support is added three containing 5.6%
The mixture of sulfur oxide and air is warming up to 35 DEG C of sulfonation as sulfonating agent, and the residence time of sulfonating agent is 0.15s, is diluted
Filter, obtains porous carbon sulfonic acid carrier.
It (3) is 1:0.002:0.01 according to porous carbon sulfonic acid carrier, stannous chloride and ferric iron molar ratio, by porous carbon sulphur
Acid vectors are placed in stannous chloride solution, after mixing evenly, are taken out, are placed in trivalent ferrous solution, and keeping system is acidity, are continued
Stirring is taken out, is spin-dried for, the high-temperature calcination at 500 DEG C, and the porous carbon sulfonic acid catalyst of load simple substance tin is obtained.
(4) the micro-nano cellulose slurry of activation is added in methylene chloride, is uniformly dispersed, is transferred in batch reactor,
The porous carbon sulfonic acid catalyst of load simple substance tin is added, it is quick with the rate of 50 DEG C/min under the stirring rate of 6000r/min
It is warming up to 40 DEG C and carries out pre- sulfonation processing 60min, then pass to sulfonating agent, with while being stirred with the rate of 12000r/min
The rate of 0.5 DEG C/min is to slowly warm up to 50 DEG C, insulation reaction 45min, and wherein the residence time of sulfonating agent is 0.1s, and reaction stops
It is rapidly decreased to room temperature after only, takes out, washs repeatedly, is dried in vacuo, obtains the porous carbon sulfonic acid catalyst based on load simple substance tin
Sulfonated cellulose water-reducing agent.
Embodiment 6:
(1) it is 2.2:1 according to the mass ratio of carbon source and silica, nano silica microsphere is impregnated in sucrose, Portugal
In grape sugar and starch solution, after being stirred at room temperature uniformly, 90 DEG C of removal solvents is warming up to, inert gas are passed through, with 5 DEG C/min
Rate be warming up to 170 DEG C, keep the temperature pre- charing 4h, be then warming up to 480 DEG C with the rate of 1 DEG C/min, heat preservation charing 2h takes
Out, the mixture of the hydrofluoric acid and nitric acid that are 98:2 with volume ratio removes silicon, and mill-drying obtains porous carbon support.
(2) it is 1.03:1 according to the molar ratio of sulfur trioxide and porous carbon support, porous carbon support is added containing 5.2%
The mixture of sulfur trioxide and air is warming up to 42 DEG C of sulfonation as sulfonating agent, and the residence time of sulfonating agent is 0.1s, is diluted
Filter, obtains porous carbon sulfonic acid carrier.
It (3) is 1:0.008:0.01 according to porous carbon sulfonic acid carrier, stannous chloride and ferric iron molar ratio, by porous carbon sulphur
Acid vectors are placed in stannous chloride solution, after mixing evenly, are taken out, are placed in trivalent ferrous solution, and keeping system is acidity, are continued
Stirring is taken out, is spin-dried for, the high-temperature calcination at 450 DEG C, and the porous carbon sulfonic acid catalyst of load simple substance tin is obtained.
(4) the micro-nano cellulose slurry of activation is added in methylene chloride, is uniformly dispersed, is transferred in batch reactor,
The porous carbon sulfonic acid catalyst of load simple substance tin is added, it is quick with the rate of 20 DEG C/min under the stirring rate of 8000r/min
It is warming up to 45 DEG C and carries out pre- sulfonation processing 30min, then pass to sulfonating agent, with while being stirred with the rate of 15000r/min
The rate of 0.3 DEG C/min is to slowly warm up to 53 DEG C, insulation reaction 15min, and wherein the residence time of sulfonating agent is 0.15s, reaction
It is rapidly decreased to room temperature after stopping, taking out, washs repeatedly, is dried in vacuo, obtains the porous carbon sulfonic acid catalysis based on load simple substance tin
The sulfonated cellulose water-reducing agent of agent.
Through detecting, the sulfonated cellulose of the porous carbon sulfonic acid catalyst based on load simple substance tin of embodiment 1-6 preparation subtracts
The surface total acid content of aqua, sulfonic acid amount, the result of sulfonation degree are as follows:
As seen from the above table, the sulfonated cellulose of the porous carbon sulfonic acid catalyst prepared by the present invention based on load simple substance tin subtracts
Sulfonic acid group rich in aqua makes the sulfonated cellulose water-reducing agent of the porous carbon sulfonic acid catalyst based on load simple substance tin
With strongly hydrophilic, also there is dispersibility and water reducing ability well, also there is certain temperature resistance and salt-resistance.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of preparation method of the sulfonated cellulose water-reducing agent of the porous carbon sulfonic acid catalyst based on load simple substance tin, feature
It is, comprising the following steps:
(1) nano silica microsphere is impregnated in carbon source solution, after being stirred at room temperature uniformly, heating removal solvent leads to
Enter inert gas, continues heating carbonization, take out, remove silicon, mill-drying obtains porous carbon support；
(2) sulfonating agent is added in the porous carbon support by step (1) preparation, and heat up sulfonation, and dilute filtration obtains porous carbon sulphur
Acid vectors；
(3) porous carbon sulfonic acid carrier prepared by step (2) is placed in stannous chloride solution, after mixing evenly, takes out, be placed in three
In valence ferrous solution, keeping system is acidity, continues to stir, and takes out, is spin-dried for, high-temperature calcination, obtains the porous carbon of load simple substance tin
Sulfonic acid catalyst；
(4) the micro-nano cellulose slurry of activation is added in methylene chloride, is uniformly dispersed, is transferred in batch reactor, is added
The porous carbon sulfonic acid catalyst of the load simple substance tin of step (3) preparation, is rapidly heated while stirring and carries out pre- sulfonation processing,
Sulfonating agent is then passed to, the heating of Huan Maning while stirring, insulation reaction is rapidly decreased to room temperature after reaction stopping, taking out, repeatedly
Washing, vacuum drying obtain the sulfonated cellulose water-reducing agent of the porous carbon sulfonic acid catalyst based on load simple substance tin.
2. a kind of sulfonated cellulose diminishing of porous carbon sulfonic acid catalyst based on load simple substance tin according to claim 1
The preparation method of agent, it is characterised in that: in the step (1), carbon source is sucrose, grape sugar and starch in carbon source solution.
3. a kind of sulfonated cellulose diminishing of porous carbon sulfonic acid catalyst based on load simple substance tin according to claim 1
The preparation method of agent, it is characterised in that: in the step (1), the mass ratio of carbon source and silica is 2-2.2:1.
4. a kind of sulfonated cellulose diminishing of porous carbon sulfonic acid catalyst based on load simple substance tin according to claim 1
The preparation method of agent, it is characterised in that: in the step (1), the technique for the carbonization that heats up are as follows: at from 90-100 DEG C, with 3-5 DEG C/
The rate of min is warming up to 170-180 DEG C, keeps the temperature pre- charing 3-4h, is then warming up to 420-480 DEG C with the rate of 1-2 DEG C/min,
Heat preservation charing 2-4h.
5. a kind of sulfonated cellulose diminishing of porous carbon sulfonic acid catalyst based on load simple substance tin according to claim 1
The preparation method of agent, it is characterised in that: in the step (1), except the solvent of silicon be volume ratio be 95-98:2-5 hydrofluoric acid and
The mixture of nitric acid.
6. a kind of sulfonated cellulose diminishing of porous carbon sulfonic acid catalyst based on load simple substance tin according to claim 1
The preparation method of agent, it is characterised in that: in the step (2), sulfonating agent is the mixture of sulfur trioxide and air, sulfur trioxide
Volume fraction be 5.2-5.6%, the molar ratio of sulfur trioxide and porous carbon support is 1-1.03:1.
7. a kind of sulfonated cellulose diminishing of porous carbon sulfonic acid catalyst based on load simple substance tin according to claim 1
The preparation method of agent, it is characterised in that: in the step (2), the temperature of the sulfonation that heats up is 35-42 DEG C, when the stop of sulfonating agent
Between be 0.1-0.15s.
8. a kind of sulfonated cellulose diminishing of porous carbon sulfonic acid catalyst based on load simple substance tin according to claim 1
The preparation method of agent, it is characterised in that: in the step (3), porous carbon sulfonic acid carrier, stannous chloride and ferric iron molar ratio are
1:0.002-0.008:0.01.
9. a kind of sulfonated cellulose diminishing of porous carbon sulfonic acid catalyst based on load simple substance tin according to claim 1
The preparation method of agent, it is characterised in that: in the step (4), the technique of heating are as follows: the load simple substance of step (4) preparation is added
The porous carbon sulfonic acid catalyst of tin is rapidly heated under the stirring rate of 6000-8000r/min with the rate of 20-50 DEG C/min
Pre- sulfonation is carried out to 40-45 DEG C and handles 30-60min, is then passed to sulfonating agent, is stirred on one side with the rate of 12000-15000r/min
It mixes and with the rate of 0.3-0.5 DEG C/min is to slowly warm up to 50-53 DEG C, insulation reaction 15-45min on one side, wherein sulfonating agent stops
Staying the time is 0.1-0.15s.
10. the sulfonated cellulose of any one porous carbon sulfonic acid catalyst based on load simple substance tin described in claim 1-9
Water-reducing agent.
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| 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 |
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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 |
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