CN106810269B - A kind of modified method and its application for preparing ceramic additive of composite biomass base - Google Patents
A kind of modified method and its application for preparing ceramic additive of composite biomass base Download PDFInfo
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- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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Abstract
The invention discloses a kind of modified method and its application for preparing ceramic additive of composite biomass base, it is mixed with starch in Catalyzed by Ultrasonic Wave using the landfill leachate after concentration, again by using alkalization, sulfonation, quaternization reaction and the powdered ceramic additive loose by the obtained black of spray drying, by carrying out alkalization and sulfonating reaction reaction after liquid and starch mixing is concentrated to landfill leachate, the activity of effective molecular structure can be improved, further quaternization reaction can be effectively controlled the molecular weight of product, make ceramic additive obtained while with good dispersion performance, ceramic green intensity can also be greatly improved, and ceramic additive produced by the present invention has dispersion, diminishing, grinding aid, the multiple functions such as cohere and defoam, the by-product of offal treatment is not only made to have obtained the effective of recycling It utilizes, the crisis of non-renewable energy resources can also be alleviated, realize the practical application value and social value of the by-product in garbage processing procedure.
Description
Technical field
The present invention relates to fine chemistry industries, environment-friendly material field, and in particular to a kind of modified preparation of composite biomass base
The method and its application of ceramic additive.
Background technique
Big country of the China as Production of Ceramics, ceramic yield occupy the first in the world for successive years, and wherein domestic ceramics produces
Amount accounts for 70% or so of global yield, and display art's ceramic yield accounts for the 65% of global yield, architectural pottery yield also Zhan Quanqiu
50% or so of total output.But since China is an energy and the relatively poor country of resource, and ceramic industry is a height
Degree relies on the industry of the energy, resource, needs to consume 100,000,000 tons of good raw mineral materials or more every year, the consumption for the energy sources is converted into standard
Coal probably needs 30,000,000 tons or more；Industry of the ceramic industry as a high energy consumption, from the firing for being prepared into product of slurry,
The cost of the energy such as electric power, the fuel of each process consumption accounts for the 23%~40% of entire Production of Ceramics cost, therefore, energy conservation drop
Consumption by be Production of Ceramics trend of the times and ceramic industry sustainable development essential condition, in Production of Ceramics, for meet
Each technique requires often to need to be added different additives, although dosage is little, plays an important role, additive additive amount
Number also influence the appearance and physical property of finished product.
In addition, the municipal refuse quantity in China increases different with Chinese society expanding economy, the quickening of urbanization process
Often rapidly, and during numerous urban garbage disposals, a large amount of rubbish air storage or landfill are not only taken up largely
Soil, and great secondary pollution easily is caused to soil, underground water, atmosphere, become serious environmental problem, since rubbish exists
It carries out that humic acid abundant can be generated during aerobic fermentation, and humic acid is a kind of unbodied organic high molecular compound,
It is modified, makes it have biggish space net structure, can be used as ceramic additive and greatly improve ceramics
Combination between grain increases ceramics strength, therefore, after landfill leachate is modified is applied to ceramic additive and produces
Field is of great significance to the using energy source environment and heat recovery that improve China.
However, there is also preparation process complexity, reaction time length, energy usage in the production of China's ceramic additive at present
Greatly, seriously polluted problem, and the ceramic additive function of being produced is more single, generally requires in application process
It is used cooperatively with other ceramic additives, improves production cost.
Summary of the invention
In order to solve the deficiencies in the prior art, the purpose of the present invention is to provide one kind make ceramics have good dispersion,
It is compound to can be improved that ceramic green intensity, production application is reliable, mild condition, the reaction time is short, rate is fast, production cost is low
Biomass-based modification prepares the method and its application of ceramic additive.
In order to realize above-mentioned technical purpose, the technical solution of the present invention is as follows: a kind of modified preparation pottery of composite biomass base
The method of porcelain additive after starch is added, passes sequentially through alkalization, sulfonation and quaternized using landfill leachate concentration liquid as raw material
It reacts and ceramic additive is made.
Further, specifically includes the following steps:
(1) liquid and starch is concentrated in landfill leachate to carry out after ultrasonic wave mixes, is added catalyst, and by system temperature
Degree is adjusted to 65~95 DEG C, and pH value is adjusted to 9~12, then is persistently stirred to react 2~6h；
(2) benzoic acid, phenol, aldehyde compound, sulfonating agent and water are sequentially added into above-mentioned solution after the reaction was completed,
And system temperature is adjusted to 70~100 DEG C, react 1.5~9h；
(3) pH adjusting agent is added into step (2) solution after the reaction was completed, by pH value of solution to being adjusted to 9~12, then will
After solution temperature is adjusted to 70~100 DEG C, quaternizing agent is added and carries out 3~6h of reaction, it is after the reaction was completed that solution is cooling, then
It is added in spray drying device and is dried by spraying, can be prepared by the loose powdered ceramic additive of black.
Further, the addO-on therapy and mass fraction of each step are as follows:
Further, landfill leachate concentration liquid passes through dense after biochemical film concentration for landfill leachate stoste
The solid content of contracting liquid, the landfill leachate concentration liquid is 10%~45%.
Further, the starch is Corn Starch, industrial potato starch, industrial wheat starch, industrial para arrowroot
At least one of powder mixes.
Further, the pH adjusting agent is sodium hydroxide, potassium carbonate, sodium carbonate, sodium citrate, potassium citrate, carbonic acid
At least one of hydrogen trisodium, sodium dihydrogen citrate, citric acid, lactic acid, tartaric acid, malic acid, metatartaric acid, sulfuric acid mixing and
At.
Further, the catalyst is zinc sulfate, zinc nitrate, copper sulphate, copper nitrate, ferric nitrate, ferrous sulfate, nitric acid
At least one of ferrous iron, iron ammonium sulfate, nickel sulfate mix.
Further, the aldehyde compound is formaldehyde, in acetaldehyde, glutaraldehyde, methacrylaldehyde, metaformaldehyde, paraformaldehyde
At least one mix.
Further, the sulfonating agent be ammonium persulfate, ammonium bisulfite, sulfamic acid, sulfuric acid, in sodium sulfite extremely
Few one kind mixes.
Further, the quaternizing agent is chloro- 2 hydroxypropyl-trimethyl ammonium chloride of 1-, dodecyl dimethyl benzyl
The mixing of at least one of ammonium chloride, octadecyldimethyl hydroxyethyl ammonium nitrate, hydrogen sulfate tetrabutylammonium, tetrabutylammonium bromide
It forms.
Further, the inlet temperature of the spray drying device is 140~350 DEG C, and outlet temperature is 70~95 DEG C, warp
The dry powder rate of recovery after spraying is greater than 95%.
Using above-mentioned technical solution, the invention has the benefit that by using after concentration landfill leachate and shallow lake
Powder mixes under Catalyzed by Ultrasonic Wave, then by using alkalization, sulfonation, quaternization reaction and by be spray-dried be made black it is loose
Powdered ceramic additive, not only process is simply controllable, and is conducive to industrialized production, by the way that landfill leachate is concentrated
Alkalization and sulfonating reaction reaction are carried out after liquid and starch mixing, the activity of effective molecular structure can be improved, it is further quaternized
Reaction can be effectively controlled the molecular weight of product, make ceramic additive obtained with the same of good dispersion performance
When, ceramic green intensity can also be greatly improved, and ceramic additive produced by the present invention has dispersion, diminishing, helps
It the multiple functions such as grinds, cohere and defoams, can also extend as dye dispersant, cement water reducing agent, drilling fluid thinner
Deng not only making the by-product of offal treatment obtain the effective use of recycling, non-renewable energy resources can also be alleviated
The practical application value and social value of the by-product in garbage processing procedure are realized in crisis.
Specific embodiment
A kind of modified method for preparing ceramic additive of composite biomass base, is concentrated liquid as raw material using landfill leachate, adds
After entering starch, passes sequentially through alkalization, sulfonation and quaternization reaction and ceramic additive is made.
Further, specifically includes the following steps:
(1) liquid and starch is concentrated in landfill leachate to carry out after ultrasonic wave mixes, is added catalyst, and by system temperature
Degree is adjusted to 65~95 DEG C, and pH value is adjusted to 9~12, then is persistently stirred to react 2~6h；
(2) benzoic acid, phenol, aldehyde compound, sulfonating agent and water are sequentially added into above-mentioned solution after the reaction was completed,
And system temperature is adjusted to 70~100 DEG C, react 1.5~9h；
(3) pH adjusting agent is added into step (2) solution after the reaction was completed, by pH value of solution to being adjusted to 9~12, then will
After solution temperature is adjusted to 70~100 DEG C, quaternizing agent is added and carries out 3~6h of reaction, it is after the reaction was completed that solution is cooling, then
It is added in spray drying device and is dried by spraying, can be prepared by the loose powdered ceramic additive of black.
Further, the addO-on therapy and mass fraction of each step are as follows:
Further, landfill leachate concentration liquid passes through dense after biochemical film concentration for landfill leachate stoste
The solid content of contracting liquid, the landfill leachate concentration liquid is 10%~45%.
Further, the starch is Corn Starch, industrial potato starch, industrial wheat starch, industrial para arrowroot
At least one of powder mixes.
Further, the pH adjusting agent is sodium hydroxide, potassium carbonate, sodium carbonate, sodium citrate, potassium citrate, carbonic acid
At least one of hydrogen trisodium, sodium dihydrogen citrate, citric acid, lactic acid, tartaric acid, malic acid, metatartaric acid, sulfuric acid mixing and
At.
Further, the catalyst is zinc sulfate, zinc nitrate, copper sulphate, copper nitrate, ferric nitrate, ferrous sulfate, nitric acid
At least one of ferrous iron, iron ammonium sulfate, nickel sulfate mix.
Further, the aldehyde compound is formaldehyde, in acetaldehyde, glutaraldehyde, methacrylaldehyde, metaformaldehyde, paraformaldehyde
At least one mix.
Further, the sulfonating agent be ammonium persulfate, ammonium bisulfite, sulfamic acid, sulfuric acid, in sodium sulfite extremely
Few one kind mixes.
Further, the quaternizing agent is chloro- 2 hydroxypropyl-trimethyl ammonium chloride of 1-, dodecyl dimethyl benzyl
The mixing of at least one of ammonium chloride, octadecyldimethyl hydroxyethyl ammonium nitrate, hydrogen sulfate tetrabutylammonium, tetrabutylammonium bromide
It forms.
Further, the inlet temperature of the spray drying device is 140~350 DEG C, and outlet temperature is 70~95 DEG C, warp
The dry powder rate of recovery after spraying is greater than 95%.
Embodiment 1
A kind of modified method for preparing ceramic additive of composite biomass base comprising following steps:
(1) liquid is concentrated in the landfill leachate that 350Kg solid content is 20% and 150Kg Corn Starch carries out ultrasonic wave
It after mixing, adds it in reactor, and 1.5Kg is added with ferric nitrate, copper nitrate and iron ammonium sulfate by 8: 1: 1
The catalyst that mass ratio mixes, and system temperature is adjusted to 70 DEG C, pH value is adjusted to 10, is persistently stirred to react
4h；
(2) sequentially added into above-mentioned solution after the reaction was completed 12Kg benzoic acid, 25Kg phenol, 50Kg with glutaraldehyde and
Aldehyde compound that paraformaldehyde in mass ratio 1: 1 mixes, 54.4Kg with ammonium sulfate and ammonium bisulfite by 1: 2 quality
100 DEG C are adjusted to than the sulfonating agent and 230.3Kg water mixed, and by system temperature, reacts 6h；
(3) quality that 26.8Kg presses 6: 1 with sodium hydroxide and sodium carbonate is added into step (2) solution after the reaction was completed
Than the pH adjusting agent mixed, by pH value of solution to being adjusted to 10, then after solution temperature is adjusted to 75 DEG C, 100Kg 1- is added
Chloro-2-hydroxypropyl-trimethyl ammonium chloride carries out reaction 3h, after the reaction was completed that solution is cooling, and being then added to device temperature is 140
DEG C, it is dried in the spray drying device that outlet temperature is 70 DEG C by spraying, can be prepared by the loose powdered ceramic of black and add
Add agent, wherein the dry powder rate of recovery after spray drying is 95.4%.
Embodiment 2
A kind of modified method for preparing ceramic additive of composite biomass base comprising following steps:
(1) liquid is concentrated in the landfill leachate that 402Kg solid content is 22% and 150Kg industry potato starch carries out ultrasonic wave
After mixing, add it in reactor, and be added 0.9Kg with nickel sulfate, ferric nitrate and ferrous sulfate by 8: 2: 1 matter
The catalyst that amount ratio mixes, and system temperature is adjusted to 80 DEG C, pH value is adjusted to 9, is persistently stirred to react 2h；
(2) 14Kg benzoic acid, 30Kg phenol, 49Kg are sequentially added into above-mentioned solution after the reaction was completed with formaldehyde, penta
Aldehyde compound that dialdehyde and paraformaldehyde in mass ratio 1: 1: 1 mix, 54.4Kg are with ammonium sulfite and ammonium bisulfite
The sulfonating agent and 134.7Kg water mixed by 3: 2 mass ratioes, and system temperature is adjusted to 95 DEG C, react 3.5h；
(3) 35Kg is added into step (2) solution after the reaction was completed with sodium carbonate sodium citrate, sodium hydroxide and carbonic acid
Solution temperature by pH value of solution to being adjusted to 10, then is adjusted to 100 by the pH adjusting agent that sodium is mixed by 6: 1: 1 mass ratio
After DEG C, be added 130Kg with the mixture of dodecyl benzyl dimethyl ammonium chloride and 1- chloro-2-hydroxypropyl-trimethyl ammonium chloride into
Row reaction 4h, after the reaction was completed that solution is cooling, being then added to device temperature is 200 DEG C, and outlet temperature is that 80 DEG C spraying does
It is dried in dry equipment by spraying, can be prepared by the loose powdered ceramic additive of black, wherein the dry powder after spray drying
The rate of recovery is 95.0%.
Embodiment 3
A kind of modified method for preparing ceramic additive of composite biomass base comprising following steps:
(1) liquid and 200Kg is concentrated with Corn Starch and industry soil in the landfill leachate that 409Kg solid content is 18%
After the starch mixture progress ultrasonic wave that beans starch is mixed by 1: 1 mass ratio mixes, add it in reactor,
And the catalysis that 0.85Kg is mixed with zinc nitrate, nickel sulfate, ferric nitrate and ferrous sulfate by 8: 1: 1: 1 mass ratio is added
Agent, and system temperature is adjusted to 95 DEG C, pH value is adjusted to 9.5, is persistently stirred to react 6h；
(2) 16Kg benzoic acid, 32Kg phenol, 46Kg are sequentially added into above-mentioned solution after the reaction was completed with formaldehyde, second
Aldehyde compound that aldehyde in mass ratio 1: 1 mixes, 58Kg are mixed with ammonium sulfite and ammonium bisulfite by 1: 1 mass ratio
Made of sulfonating agent and 53.15Kg water, and system temperature is adjusted to 85 DEG C, reacts 1.5h；
(3) 45Kg is added into step (2) solution after the reaction was completed and presses 6: 1 with potassium carbonate, sodium hydroxide and sodium carbonate:
The pH adjusting agent that 1 mass ratio mixes is added by pH value of solution to being adjusted to 10, then after solution temperature is adjusted to 70 DEG C
140Kg is reacted with the mixture of dodecyl benzyl dimethyl ammonium chloride and dodecyl dimethyl hydroxyethyl ammonium nitrate
5h, after the reaction was completed that solution is cooling, being then added to device temperature is 350 DEG C, the spray drying device that outlet temperature is 95 DEG C
In be dried spraying, can be prepared by the loose powdered ceramic additive of black, wherein the dry powder rate of recovery after spray drying
It is 97.1%.
Embodiment 4
A kind of modified method for preparing ceramic additive of composite biomass base comprising following steps:
(1) liquid is concentrated in the landfill leachate that 460Kg solid content is 26% and 180Kg is small with Corn Starch and industry
After the starch mixture progress ultrasonic wave that wheat starch is mixed by 1: 1 mass ratio mixes, add it in reactor,
And the catalyst that 1Kg is mixed with zinc nitrate, nickel sulfate, ferric nitrate and copper nitrate by 8: 1: 1: 1 mass ratio is added, and will
System temperature is adjusted to 80 DEG C, and pH value is adjusted to 12, is persistently stirred to react 5h；
(2) 12Kg benzoic acid, 28Kg phenol, 58Kg are sequentially added into above-mentioned solution after the reaction was completed with formaldehyde and third
Aldehyde compound that olefin(e) acid in mass ratio 1: 1 mixes, 53Kg are mixed by 1: 1 mass ratio with ammonium persulfate and ammonium bisulfite
Sulfonating agent made of conjunction and 23Kg water, and system temperature is adjusted to 90 DEG C, react 7h；
(3) be added into step (2) solution after the reaction was completed 45Kg with sodium sesquicarbonate, potassium carbonate, sodium hydroxide and
The pH adjusting agent that sodium carbonate is mixed by 3: 1: 1: 1 mass ratio by pH value of solution to being adjusted to 11, then solution temperature is adjusted
To after 75 DEG C, 140Kg is added and is carried out instead with the mixture of hydrogen sulfate tetrabutylammonium and dodecyl dimethyl hydroxyethyl ammonium nitrate
6h is answered, after the reaction was completed that solution is cooling, being then added to device temperature is 300 DEG C, and outlet temperature is that 85 DEG C of spray drying is set
It is dried in standby by spraying, can be prepared by the loose powdered ceramic additive of black, wherein the dry powder recycling after spray drying
Rate is 98.3%.
Embodiment 5
A kind of modified method for preparing ceramic additive of composite biomass base comprising following steps:
(1) liquid is concentrated in the landfill leachate that 480Kg solid content is 10% and 200Kg is small with industrial potato starch and industry
After the starch mixture progress ultrasonic wave that wheat starch is mixed by 1: 1 mass ratio mixes, add it in reactor,
And 0.75Kg is added and is urged with zinc sulfate, ferrous sulfate, iron ammonium sulfate and copper nitrate by what 8: 1: 1: 1 mass ratio mixed
Agent, and system temperature is adjusted to 65 DEG C, pH value is adjusted to 10, is persistently stirred to react 4h；
(2) 10Kg benzoic acid, 24Kg phenol, 50Kg are sequentially added into above-mentioned solution after the reaction was completed with acetaldehyde and three
Aldehyde compound that polyformaldehyde in mass ratio 1: 1 mixes, 46Kg are mixed by 1: 1 mass ratio with ammonium persulfate and sulfamic acid
Sulfonating agent made of conjunction and 34.25Kg water, and system temperature is adjusted to 100 DEG C, react 8h；
(3) 55Kg is added into step (2) solution after the reaction was completed with sodium carbonate sodium citrate, potassium citrate, carbonic acid
Solution temperature by pH value of solution to being adjusted to 12, then is adjusted to 90 by the pH adjusting agent that sodium is mixed by 3: 1: 1: 1 mass ratio
After DEG C, 100Kg is added with the mixture of tetrabutylammonium bromide and dodecyl dimethyl hydroxyethyl ammonium nitrate and carries out reaction 5h, instead
Should be cooling by solution after the completion, being then added to device temperature is 256 DEG C, is carried out in the spray drying device that outlet temperature is 83 DEG C
It is dry spraying, it can be prepared by the loose powdered ceramic additive of black, wherein the dry powder rate of recovery after spray drying is
96.3%.
Embodiment 6
A kind of modified method for preparing ceramic additive of composite biomass base comprising following steps:
(1) liquid is concentrated in the landfill leachate that 385Kg solid content is 31% and 170Kg is small with industrial tapioca and industry
After the starch mixture progress ultrasonic wave that wheat starch is mixed by 1: 1 mass ratio mixes, add it in reactor,
And 0.65Kg is added and is urged with nickel sulfate, ferrous sulfate, ferrous nitrate ammonium and copper nitrate by what 8: 1: 1: 1 mass ratio mixed
Agent, and system temperature is adjusted to 85 DEG C, pH value is adjusted to 11, is persistently stirred to react 5h；
(2) 13Kg benzoic acid, 21Kg phenol, 50Kg are sequentially added into above-mentioned solution after the reaction was completed with acetaldehyde and more
Aldehyde compound that polyformaldehyde in mass ratio 1: 1 mixes, 49Kg are mixed by 1: 1 mass ratio with ammonium persulfate and sodium sulfite
Sulfonating agent made of conjunction and 150.35Kg water, and system temperature is adjusted to 90 DEG C, react 5h；
(3) 51Kg is added into step (2) solution after the reaction was completed with sodium hydroxide, sodium carbonate sodium citrate and carbonic acid
Solution temperature by pH value of solution to being adjusted to 11, then is adjusted to 75 DEG C by the pH adjusting agent that sodium is mixed by 3: 1: 1 mass ratio
Afterwards, 110Kg is added and reaction 6h is carried out with the mixture of tetrabutylammonium bromide and 1- chloro-2-hydroxypropyl-trimethyl ammonium chloride, react
After the completion that solution is cooling, being then added to device temperature is 180 DEG C, is done in the spray drying device that outlet temperature is 75 DEG C
It is dry spraying, it can be prepared by the loose powdered ceramic additive of black, wherein the dry powder rate of recovery after spray drying is 95.8%.
Embodiment 7
A kind of modified method for preparing ceramic additive of composite biomass base comprising following steps:
(1) liquid and 220Kg is concentrated with industrial tapioca and industry jade in the landfill leachate that 315Kg solid content is 23%
After the starch mixture progress ultrasonic wave that rice starch is mixed by 1: 1 mass ratio mixes, add it in reactor,
And the catalyst that 1.4Kg is mixed with nickel sulfate, ferric sulfate by 1: 1 mass ratio is added, and system temperature is adjusted to 65
DEG C, pH value is adjusted to 10.5, is persistently stirred to react 5h；
(2) sequentially added into above-mentioned solution after the reaction was completed 19Kg benzoic acid, 28Kg phenol, 61Kg with glutaraldehyde and
Aldehyde compound that metaformaldehyde in mass ratio 1: 1 mixes, 65Kg are mixed by 1: 1 mass ratio with the concentrated sulfuric acid and sodium sulfite
Sulfonating agent made of conjunction and 60.6Kg water, and system temperature is adjusted to 70 DEG C, react 9h；
(3) mass ratio that 65Kg presses 3: 1 with sodium hydroxide, sodium carbonate is added into step (2) solution after the reaction was completed
165Kg is added by pH value of solution to being adjusted to 9, then after solution temperature is adjusted to 85 DEG C with 1- in the pH adjusting agent mixed
The mixture of chloro-2-hydroxypropyl-trimethyl ammonium chloride and dodecyl dimethyl hydroxyethyl ammonium nitrate carries out reaction 5h, has reacted
After that solution is cooling, being then added to device temperature is 210 DEG C, is dried in the spray drying device that outlet temperature is 86 DEG C
It is spraying, it can be prepared by the loose powdered ceramic additive of black, wherein the dry powder rate of recovery after spray drying is 96.5%.
Embodiment 8
A kind of modified method for preparing ceramic additive of composite biomass base comprising following steps:
(1) liquid and 150Kg is concentrated with industrial potato starch and industry jade in the landfill leachate that 550Kg solid content is 45%
After the starch mixture progress ultrasonic wave that rice starch is mixed by 1: 1 mass ratio mixes, add it in reactor,
And the catalyst that 1.1Kg is mixed with ferrous sulfate, ferric sulfate by 1: 1 mass ratio is added, and system temperature is adjusted to
85 DEG C, pH value is adjusted to 9.5, is persistently stirred to react 5h；
(2) sequentially added into above-mentioned solution after the reaction was completed 23Kg benzoic acid, 21Kg phenol, 50Kg with methacrylaldehyde and
Aldehyde compound that paraformaldehyde in mass ratio 1: 1 mixes, 40Kg are mixed by 1: 1 mass ratio with the concentrated sulfuric acid and ammonium persulfate
Sulfonating agent made of conjunction and 29.9Kg water, and system temperature is adjusted to 70 DEG C, react 6h；
(3) quality that 75Kg presses 2: 1 with sodium hydroxide, sodium bicarbonate is added into step (2) solution after the reaction was completed
Than the pH adjusting agent mixed, by pH value of solution to being adjusted to 10, then after solution temperature is adjusted to 90 DEG C, 60Kg 12 is added
Alkyl dimethyl hydroxyethyl ammonium nitrate carries out reaction 6h, after the reaction was completed that solution is cooling, and being then added to device temperature is 320
DEG C, it is dried in the spray drying device that outlet temperature is 92 DEG C by spraying, can be prepared by the loose powdered ceramic of black and add
Add agent, wherein the dry powder rate of recovery after spray drying is 97.8%.
Performance test
By ceramic additive made from Examples 1 to 8 and common additive (sodium tripolyphosphate and water glass currently on the market
Glass in mass ratio 5: 2 mixes) it compares, it is added into the ceramic batch being formulated as shown in the table and uses:
| ZhangZhou clay | 45% |
| Kaolin | 30% |
| Montmorillonite | 15% |
| Silica flour | 10% |
Contrast sample obtained and Examples 1 to 8 are carried out to be tested for the property comparison, gained knot using sample obtained
Fruit is as follows:
Note:
1. the delivery time of ceramic sauce, the time used in 100 milliliters of slurries of outflow indicated using -4 glasss of measurements are applied；
2. the test of green compact flexural strength is referring to the world the 4th part GBT3810.4-2006: the modulus of rupture and breakdown strength
Measurement.
The above is the embodiment of the present invention, for the ordinary skill in the art, religion according to the present invention
Lead, without departing from the principles and spirit of the present invention all equivalent changes done according to scope of the present invention patent, repair
Change, replacement and variant, is all covered by the present invention.
Claims (9)
1. a kind of modified method for preparing ceramic additive of composite biomass base, it is characterised in that: liquid is concentrated with landfill leachate
For raw material, after starch is added, passes sequentially through alkalization, sulfonation and quaternization reaction and ceramic additive is made；
Itself specifically includes the following steps:
(1) liquid and starch is concentrated in landfill leachate to carry out after ultrasonic wave mixes, is added catalyst, and by system temperature tune
For section to 65~95 DEG C, pH value is adjusted to 9~12, then is persistently stirred to react 2~6h；
(2) benzoic acid, phenol, aldehyde compound, sulfonating agent and water are sequentially added into above-mentioned solution after the reaction was completed, and will
System temperature is adjusted to 70~100 DEG C, reacts 1.5~9h；
(3) pH adjusting agent is added into step (2) solution after the reaction was completed, by pH value of solution to being adjusted to 9~12, then by solution
After temperature is adjusted to 70~100 DEG C, quaternizing agent is added and carries out 3~6h of reaction, it is after the reaction was completed that solution is cooling, it adds
It is dried into spray drying device by spraying, can be prepared by the loose powdered ceramic additive of black.
2. a kind of modified method for preparing ceramic additive of composite biomass base according to claim 1, it is characterised in that:
The addO-on therapy and mass fraction of each step are as follows:
Liquid 35%~55% is concentrated in landfill leachate；
Starch 15%~22%；
Catalyst 0.065%~0.15%；
PH adjusting agent 2.68%~7.5%；
Benzoic acid 1.2%~2.3%；
Phenol 2.1%~3.2%；
Aldehyde compound 4.6%~6.1%；
Sulfonating agent 4%~6.5%；
Quaternizing agent 6%~16.5%
Water 2.3%~23.03%.
3. a kind of modified method for preparing ceramic additive of composite biomass base according to claim 1 or 2, feature exist
In: the landfill leachate concentration liquid is landfill leachate stoste by the concentrate after biochemical film concentration, described
The solid content that liquid is concentrated in landfill leachate is 10%~45%.
4. a kind of modified method for preparing ceramic additive of composite biomass base according to claim 1 or 2, feature exist
In: the starch be Corn Starch, industrial potato starch, industrial wheat starch, at least one in industrial tapioca
Kind mixes.
5. a kind of modified method for preparing ceramic additive of composite biomass base according to claim 1 or 2, feature exist
In: the pH adjusting agent is sodium hydroxide, potassium carbonate, sodium carbonate, sodium citrate, potassium citrate, sodium sesquicarbonate, citric acid
At least one of one sodium, citric acid, lactic acid, tartaric acid, malic acid, metatartaric acid, sulfuric acid mix.
6. a kind of modified method for preparing ceramic additive of composite biomass base according to claim 1 or 2, feature exist
In: the catalyst is zinc sulfate, zinc nitrate, copper sulphate, copper nitrate, ferric nitrate, ferrous sulfate, ferrous nitrate, sulfuric acid Asia
At least one of iron ammonium, nickel sulfate mix.
7. a kind of modified method for preparing ceramic additive of composite biomass base according to claim 1 or 2, feature exist
In: the aldehyde compound is mixed at least one of formaldehyde, acetaldehyde, glutaraldehyde, methacrylaldehyde, metaformaldehyde, paraformaldehyde
It closes；The quaternizing agent is chloro- 2 hydroxypropyl-trimethyl ammonium chloride of 1-, dodecyl benzyl dimethyl ammonium chloride, ten
At least one of eight alkyl dimethyl hydroxyethyl ammonium nitrates, hydrogen sulfate tetrabutylammonium, tetrabutylammonium bromide mix.
8. a kind of modified method for preparing ceramic additive of composite biomass base according to claim 1 or 2, feature exist
In: the quaternizing agent is chloro- 2 hydroxypropyl-trimethyl ammonium chloride of 1-, dodecyl benzyl dimethyl ammonium chloride, octadecane
At least one of base dimethyl hydroxy ethyl ammonium nitrate, hydrogen sulfate tetrabutylammonium, tetrabutylammonium bromide mix.
9. a kind of modified method for preparing ceramic additive of composite biomass base according to claim 1 or 2, feature exist
In: the device temperature of the spray drying device is 140~350 DEG C, and outlet temperature is 70~95 DEG C, the dry powder after spraying
The rate of recovery is greater than 95%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990392A (en) * | 2005-12-07 | 2007-07-04 | 中国科学院成都有机化学有限公司 | High degree of substitution quaternary ammonium cationic starch flocculating agent and method for synthesizing same |
| CN101033260A (en) * | 2006-03-10 | 2007-09-12 | 四平帝达变性淀粉有限公司 | Method of preparing quaternary ammonium type cationic starch |
| AU2008300605A1 (en) * | 2007-09-18 | 2009-03-26 | Akzo Nobel N.V. | Mixture containing quaternary ammonium compound and its use |
| CN104672469A (en) * | 2015-03-17 | 2015-06-03 | 福州大学 | Quaternization lignin-base dispersing agent and preparation process and application thereof |
| CN105418079A (en) * | 2015-10-29 | 2016-03-23 | 福州大学 | Biomass-based dispersant prepared by using landfill leachate and method for preparing biomass-based dispersant and application of biomass-based dispersant |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990392A (en) * | 2005-12-07 | 2007-07-04 | 中国科学院成都有机化学有限公司 | High degree of substitution quaternary ammonium cationic starch flocculating agent and method for synthesizing same |
| CN101033260A (en) * | 2006-03-10 | 2007-09-12 | 四平帝达变性淀粉有限公司 | Method of preparing quaternary ammonium type cationic starch |
| AU2008300605A1 (en) * | 2007-09-18 | 2009-03-26 | Akzo Nobel N.V. | Mixture containing quaternary ammonium compound and its use |
| CN104672469A (en) * | 2015-03-17 | 2015-06-03 | 福州大学 | Quaternization lignin-base dispersing agent and preparation process and application thereof |
| CN105418079A (en) * | 2015-10-29 | 2016-03-23 | 福州大学 | Biomass-based dispersant prepared by using landfill leachate and method for preparing biomass-based dispersant and application of biomass-based dispersant |
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