CN106810269A - A kind of composite biomass base is modified and prepares method and its application of ceramic additive - Google Patents
A kind of composite biomass base is modified and prepares method and its application of ceramic additive Download PDFInfo
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- C04B35/626—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
- 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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- 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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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—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
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- C08B31/00—Preparation of derivatives of starch
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
It is modified the invention discloses a kind of composite biomass base and prepares method and its application of ceramic additive,Mixed in Catalyzed by Ultrasonic Wave with starch using the percolate after concentration,Again by using alkalization,Sulfonation,Quaterisation and the powdered ceramic additive loose by being spray-dried prepared black,Alkalized after liquid and starch mixing are concentrated to percolate and sulfonating reaction is reacted,The activity of effective molecular structure can be improved,Further quaterisation can be effectively controlled the molecular weight of product,Make obtained ceramic additive while with good dispersive property,Ceramic green intensity can also be greatly improved,And obtained ceramic additive of the invention has dispersion,Diminishing,Grinding aid,Cohere and various functions such as froth breaking,Not only so that the accessory substance of offal treatment has obtained effective utilization of resource,The crisis of non-renewable energy resources can also be alleviated,Realize the actual application value and social value of the accessory substance in garbage processing procedure.
Description
Technical field
The present invention relates to fine chemistry industry, environment-friendly material field, and in particular to a kind of composite biomass base is modified to be prepared
The method of ceramic additive and its application.
Background technology
China as Production of Ceramics big country, ceramic yield occupies the first in the world for successive years, and wherein domestic ceramics is produced
Amount accounts for 70% or so of global yield, and display art ceramic yield accounts for the 65% of global yield, and architectural pottery yield also accounts for the whole world
50% or so of total output.But because China is an energy and the relatively poor country of resource, and ceramic industry is one high
Degree relies on the energy, the industry of resource, needs to consume more than 100,000,000 tons of the raw mineral materials of high-quality every year, and the consumption for the energy sources is converted into standard
Coal probably needs more than 30,000,000 tons；Ceramic industry is prepared into burning till for product as an industry for high energy consumption from slurry,
The electric power of each operation consumption, the cost of fuel equal energy source account for the 23%~40% of whole Production of Ceramics cost, therefore, energy-conservation drop
Consumption will be the trend of the times of Production of Ceramics, be also the essential condition of ceramic industry sustainable development, in Production of Ceramics, to meet
Each technological requirement often needs to add different additives, although consumption less, but plays an important role, additive addition
Number also have influence on the outward appearance and physical property of finished product.
In addition, with Chinese society expanding economy, the quickening of urbanization process, the municipal refuse quantity of China increases different
It is often rapid, and during numerous urban garbage disposals, substantial amounts of rubbish air storage or landfill do not only take up largely
Soil, and great secondary pollution easily is caused to soil, underground water, air, as serious environmental problem, because rubbish exists
Carry out that during aerobic fermentation abundant humic acid can be produced, and humic acid is a kind of unbodied organic high molecular compound,
It is modified, is made it have larger space net structure, can comes greatly to improve ceramics as ceramic additive
Combination between grain, increases ceramics strength, therefore, ceramic additive production is applied to after percolate is modified
Field is significant to improving the using energy source environment and heat recovery of China.
However, also existing in the production of China's ceramic additive at present, preparation technology is complicated, the reaction time is long, energy usage
Greatly, with serious pollution problem, and the ceramic additive function of being produced is more single, is generally required in application process
Used cooperatively with other ceramic additives, improve production cost.
The content of the invention
In order to solve the deficiencies in the prior art, it is an object of the invention to provide one kind make ceramics have good dispersion,
Ceramic green intensity, production application reliability can be improved, mild condition, the reaction time is short, speed is fast, low production cost compound
Biomass-based modified method and its application for preparing ceramic additive.
In order to realize above-mentioned technical purpose, the technical scheme is that：A kind of composite biomass base is modified to prepare pottery
The method of porcelain additive, liquid is concentrated as raw material with percolate, after adding starch, passes sequentially through alkalization, sulfonation and quaternized
Reaction is obtained ceramic additive.
Further, it specifically includes following steps：
(1) percolate is concentrated into liquid and starch is carried out after ultrasonic wave mixes, and adds catalyst, and by system temperature
To 65~95 DEG C, pH value is adjusted to 9~12, then carries out lasting 2~6h of stirring reaction for degree regulation；
(2) toward sequentially adding benzoic acid, phenol, aldehyde compound, sulfonating agent and water in the solution after the completion of above-mentioned reaction,
And adjust to 70~100 DEG C system temperature, react 1.5~9h；
(3) pH adjusting agent is added in the solution after the completion of being reacted toward step (2), by pH value of solution to regulation to 9~12, then will
Solution temperature is adjusted to after 70~100 DEG C, adds quaternizing agent to carry out 3~6h of reaction, cools down solution after the completion of reaction, then
It is added in spray drying device and is dried spraying, you can the loose powdered ceramic additive of black is obtained.
Further, the addO-on therapy and mass fraction of each step are as follows：
Further, described percolate concentration liquid is percolate stoste by dense after biochemical film concentration
Contracting liquid, the solid content of described percolate concentration liquid is 10%~45%.
Further, described starch is Corn Starch, industrial potato starch, industrial wheat starch, industrial para arrowroot
At least one in powder is mixed.
Further, described pH adjusting agent is NaOH, potassium carbonate, sodium carbonate, sodium citrate, potassium citrate, carbonic acid
At least one mixing in hydrogen trisodium, sodium dihydrogen citrate, citric acid, lactic acid, tartaric acid, malic acid, metatartaric acid, sulfuric acid and
Into.
Further, described catalyst is zinc sulfate, zinc nitrate, copper sulphate, copper nitrate, ferric nitrate, ferrous sulfate, nitric acid
At least one in ferrous iron, iron ammonium sulfate, nickel sulfate is mixed.
Further, described aldehyde compound is in formaldehyde, acetaldehyde, glutaraldehyde, methacrylaldehyde, metaformaldehyde, paraformaldehyde
At least one mix.
Further, described sulfonating agent be ammonium persulfate, ammonium bisulfite, sulfamic acid, sulfuric acid, sodium sulfite in extremely
Few one kind is mixed.
Further, described quaternizing agent is chloro- 2 hydroxypropyl-trimethyl ammonium chlorides of 1-, dodecyl dimethyl benzyl
At least one mixing in ammonium chloride, octadecyldimethyl hydroxyethyl ammonium nitrate, hydrogen sulfate TBuA, TBAB
Form.
Further, the inlet temperature of described 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 more than 95%.
Using above-mentioned technical scheme, beneficial effects of the present invention are：Percolate and shallow lake after using concentration
Powder mixes under Catalyzed by Ultrasonic Wave, then by using alkalization, sulfonation, quaterisation and loose by the prepared black of spray drying
Powdered ceramic additive, not only process is simply controllable, and is conducive to industrialized production, is concentrated by percolate
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 obtained ceramic additive with the same of good dispersive property
When, ceramic green intensity can also be greatly improved, and the obtained ceramic additive of the present invention has dispersion, diminishing, helps
Grind, cohere and various functions such as froth breaking, can also extend as dye dispersant, cement water reducing agent, drilling fluid thinner
Deng not only causing that the accessory substance of offal treatment has obtained effective utilization of resource, can also alleviate non-renewable energy resources
Crisis, realizes the actual application value and social value of the accessory substance in garbage processing procedure.
Specific embodiment
A kind of composite biomass base is modified the method for preparing ceramic additive, and liquid is concentrated as raw material with percolate, plus
After entering starch, pass sequentially through alkalization, sulfonation and quaterisation and ceramic additive is obtained.
Further, it specifically includes following steps：
(1) percolate is concentrated into liquid and starch is carried out after ultrasonic wave mixes, and adds catalyst, and by system temperature
To 65~95 DEG C, pH value is adjusted to 9~12, then carries out lasting 2~6h of stirring reaction for degree regulation；
(2) toward sequentially adding benzoic acid, phenol, aldehyde compound, sulfonating agent and water in the solution after the completion of above-mentioned reaction,
And adjust to 70~100 DEG C system temperature, react 1.5~9h；
(3) pH adjusting agent is added in the solution after the completion of being reacted toward step (2), by pH value of solution to regulation to 9~12, then will
Solution temperature is adjusted to after 70~100 DEG C, adds quaternizing agent to carry out 3~6h of reaction, cools down solution after the completion of reaction, then
It is added in spray drying device and is dried spraying, you can the loose powdered ceramic additive of black is obtained.
Further, the addO-on therapy and mass fraction of each step are as follows：
Further, described percolate concentration liquid is percolate stoste by dense after biochemical film concentration
Contracting liquid, the solid content of described percolate concentration liquid is 10%~45%.
Further, described starch is Corn Starch, industrial potato starch, industrial wheat starch, industrial para arrowroot
At least one in powder is mixed.
Further, described pH adjusting agent is NaOH, potassium carbonate, sodium carbonate, sodium citrate, potassium citrate, carbonic acid
At least one mixing in hydrogen trisodium, sodium dihydrogen citrate, citric acid, lactic acid, tartaric acid, malic acid, metatartaric acid, sulfuric acid and
Into.
Further, described catalyst is zinc sulfate, zinc nitrate, copper sulphate, copper nitrate, ferric nitrate, ferrous sulfate, nitric acid
At least one in ferrous iron, iron ammonium sulfate, nickel sulfate is mixed.
Further, described aldehyde compound is in formaldehyde, acetaldehyde, glutaraldehyde, methacrylaldehyde, metaformaldehyde, paraformaldehyde
At least one mix.
Further, described sulfonating agent be ammonium persulfate, ammonium bisulfite, sulfamic acid, sulfuric acid, sodium sulfite in extremely
Few one kind is mixed.
Further, described quaternizing agent is chloro- 2 hydroxypropyl-trimethyl ammonium chlorides of 1-, dodecyl dimethyl benzyl
At least one mixing in ammonium chloride, octadecyldimethyl hydroxyethyl ammonium nitrate, hydrogen sulfate TBuA, TBAB
Form.
Further, the inlet temperature of described 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 more than 95%.
Embodiment 1
A kind of composite biomass base is modified the method for preparing ceramic additive, and it is comprised the following steps：
(1) percolate that 350Kg solid contents are 20% is concentrated into liquid and 150Kg Corn Starches carries out ultrasonic wave
After mixing, in adding it to reactor, and add 1.5Kg with ferric nitrate, copper nitrate and iron ammonium sulfate by 8: 1: 1
The catalyst that mass ratio is mixed, and system temperature is adjusted to 70 DEG C, pH value is adjusted to 10, carries out lasting stirring reaction
4h；
(2) toward sequentially adding 12Kg benzoic acid, 25Kg phenol, 50Kg in the solution after the completion of above-mentioned reaction with glutaraldehyde and
Aldehyde compound that paraformaldehyde in mass ratio 1: 1 is mixed, 54.4Kg with ammonium sulfate and ammonium bisulfite by 1: 2 quality
Than the sulfonating agent and 230.3Kg water that mix, and system temperature is adjusted to 100 DEG C, react 6h；
(3) 6: 1 quality is pressed with NaOH and sodium carbonate toward addition 26.8Kg in the solution after the completion of step (2) reaction
Than the pH adjusting agent for mixing, by pH value of solution to regulation to 10, then solution temperature is adjusted to after 75 DEG C, add 100Kg 1-
Chloro-2-hydroxypropyl-trimethyl ammonium chloride carries out reaction 3h, cools down solution after the completion of reaction, and it is 140 to be then added to device temperature
DEG C, outlet temperature is to be dried spraying in 70 DEG C of spray drying device, you can the loose powdered ceramic of black is obtained and adds
Plus agent, wherein the dry powder rate of recovery after spray drying is 95.4%.
Embodiment 2
A kind of composite biomass base is modified the method for preparing ceramic additive, and it is comprised the following steps：
(1) percolate that 402Kg solid contents are 22% is concentrated into liquid and 150Kg industry potato starches carries out ultrasonic wave
After mixing, in adding it to reactor, and add 0.9Kg with nickel sulfate, ferric nitrate and ferrous sulfate by 8: 2: 1 matter
The catalyst that amount ratio is mixed, and system temperature is adjusted to 80 DEG C, pH value is adjusted to 9, carries out lasting stirring reaction 2h；
(2) toward sequentially adding 14Kg benzoic acid, 30Kg phenol, 49Kg with formaldehyde, penta in the solution after the completion of above-mentioned reaction
Aldehyde compound, the 54.4Kg that dialdehyde and paraformaldehyde in mass ratio 1: 1: 1 is mixed 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) toward addition 35Kg in the solution after the completion of step (2) reaction with sodium carbonate sodium citrate, NaOH and carbonic acid
The pH adjusting agent that sodium is mixed by 6: 1: 1 mass ratio, by pH value of solution to regulation to 10, then solution temperature is adjusted to 100
After DEG C, 130Kg is added to enter with the mixture of dodecyl benzyl dimethyl ammonium chloride and 1- chloro-2-hydroxypropyl-trimethyl ammonium chlorides
Row reaction 4h, cools down solution after the completion of reaction, and it is 200 DEG C to be then added to device temperature, and outlet temperature is that 80 DEG C of spraying is done
Spraying is dried in dry equipment, you can the loose powdered ceramic additive of black is obtained, wherein the dry powder after spray drying
The rate of recovery is 95.0%.
Embodiment 3
A kind of composite biomass base is modified the method for preparing ceramic additive, and it is comprised the following steps：
(1) percolate that 409Kg solid contents are 18% is concentrated into liquid and 200Kg with Corn Starch and industry soil
Beans starch is carried out after ultrasonic wave mixes by the starch mixture that 1: 1 mass ratio is mixed into, in adding it to reactor,
And add the catalysis that 0.85Kg mixes with zinc nitrate, nickel sulfate, ferric nitrate and ferrous sulfate by 8: 1: 1: 1 mass ratio
Agent, and system temperature is adjusted to 95 DEG C, pH value is adjusted to 9.5, carries out lasting stirring reaction 6h；
(2) toward sequentially adding 16Kg benzoic acid, 32Kg phenol, 46Kg with formaldehyde, second in the solution after the completion of above-mentioned reaction
Aldehyde compound that aldehyde in mass ratio 1: 1 is mixed, 58Kg are mixed with ammonium sulfite and ammonium bisulfite by 1: 1 mass ratio
Sulfonating agent and 53.15Kg water, and system temperature is adjusted to 85 DEG C, react 1.5h；
(3) add 45Kg with potassium carbonate, NaOH and sodium carbonate by 6: 1 in the solution after the completion of being reacted toward step (2):
The pH adjusting agent that 1 mass ratio is mixed, by pH value of solution to regulation to 10, then solution temperature is adjusted to after 70 DEG C, is added
140Kg is reacted with the mixture of dodecyl benzyl dimethyl ammonium chloride and dodecyl dimethyl hydroxyethyl ammonium nitrate
5h, cools down solution after the completion of reaction, is then added to device temperature for 350 DEG C, and outlet temperature is 95 DEG C of spray drying device
In be dried spraying, you can the loose powdered ceramic additive of black is obtained, wherein the dry powder rate of recovery after spray drying
It is 97.1%.
Embodiment 4
A kind of composite biomass base is modified the method for preparing ceramic additive, and it is comprised the following steps：
(1) percolate that 460Kg solid contents are 26% is concentrated into liquid and 180Kg is small with Corn Starch and industry
Wheat starch is carried out after ultrasonic wave mixes by the starch mixture that 1: 1 mass ratio is mixed into, in adding it to reactor,
And the catalyst that 1Kg mixes 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, carries out lasting stirring reaction 5h；
(2) toward sequentially adding 12Kg benzoic acid, 28Kg phenol, 58Kg with formaldehyde and third in the solution after the completion of above-mentioned reaction
Aldehyde compound that olefin(e) acid in mass ratio 1: 1 is mixed, 53Kg are mixed with ammonium persulfate and ammonium bisulfite by 1: 1 mass ratio
The sulfonating agent and 23Kg water for closing, and system temperature is adjusted to 90 DEG C, react 7h；
(3) toward step (2) reaction after the completion of solution in add 45Kg with sodium sesquicarbonate, potassium carbonate, NaOH and
The pH adjusting agent that sodium carbonate is mixed by 3: 1: 1: 1 mass ratio, by pH value of solution to regulation to 11, then solution temperature is adjusted
To after 75 DEG C, 140Kg is added to be carried out instead with the mixture of hydrogen sulfate TBuA and dodecyl dimethyl hydroxyethyl ammonium nitrate
6h is answered, solution is cooled down after the completion of reaction, device temperature is then added to for 300 DEG C, outlet temperature is that 85 DEG C of spray drying sets
Spraying is dried in standby, you can the loose powdered ceramic additive of black is obtained, wherein the dry powder after spray drying is reclaimed
Rate is 98.3%.
Embodiment 5
A kind of composite biomass base is modified the method for preparing ceramic additive, and it is comprised the following steps：
(1) percolate that 480Kg solid contents are 10% is concentrated into liquid and 200Kg is small with industrial potato starch and industry
Wheat starch is carried out after ultrasonic wave mixes by the starch mixture that 1: 1 mass ratio is mixed into, in adding it to reactor,
And add 0.75Kg with zinc sulfate, ferrous sulfate, iron ammonium sulfate and copper nitrate by urging that 8: 1: 1: 1 mass ratio is mixed
Agent, and system temperature is adjusted to 65 DEG C, pH value is adjusted to 10, carries out lasting stirring reaction 4h；
(2) toward sequentially adding 10Kg benzoic acid, 24Kg phenol, 50Kg with acetaldehyde and three in the solution after the completion of above-mentioned reaction
Aldehyde compound that polyformaldehyde in mass ratio 1: 1 is mixed, 46Kg are mixed with ammonium persulfate and sulfamic acid by 1: 1 mass ratio
The sulfonating agent and 34.25Kg water for closing, and system temperature is adjusted to 100 DEG C, react 8h；
(3) toward addition 55Kg in the solution after the completion of step (2) reaction with sodium carbonate sodium citrate, potassium citrate, carbonic acid
The pH adjusting agent that sodium is mixed by 3: 1: 1: 1 mass ratio, by pH value of solution to regulation to 12, then solution temperature is adjusted to 90
After DEG C, 100Kg is added to carry out reaction 5h with the mixture of TBAB and dodecyl dimethyl hydroxyethyl ammonium nitrate, instead
Should after the completion of solution is cooled down, be then added to device temperature for 256 DEG C, outlet temperature is to carry out in 83 DEG C of spray drying device
Spraying is dried, you can the loose powdered ceramic additive of black is obtained, wherein the dry powder rate of recovery after spray drying is
96.3%.
Embodiment 6
A kind of composite biomass base is modified the method for preparing ceramic additive, and it is comprised the following steps：
(1) percolate that 385Kg solid contents are 31% is concentrated into liquid and 170Kg is small with industrial tapioca and industry
Wheat starch is carried out after ultrasonic wave mixes by the starch mixture that 1: 1 mass ratio is mixed into, in adding it to reactor,
And add 0.65Kg with nickel sulfate, ferrous sulfate, ferrous nitrate ammonium and copper nitrate by urging that 8: 1: 1: 1 mass ratio is mixed
Agent, and system temperature is adjusted to 85 DEG C, pH value is adjusted to 11, carries out lasting stirring reaction 5h；
(2) toward sequentially adding 13Kg benzoic acid, 21Kg phenol, 50Kg in the solution after the completion of above-mentioned reaction with acetaldehyde and many
Aldehyde compound that polyformaldehyde in mass ratio 1: 1 is mixed, 49Kg are mixed with ammonium persulfate and sodium sulfite by 1: 1 mass ratio
The sulfonating agent and 150.35Kg water for closing, and system temperature is adjusted to 90 DEG C, react 5h；
(3) toward addition 51Kg in the solution after the completion of step (2) reaction with NaOH, sodium carbonate sodium citrate and carbonic acid
The pH adjusting agent that sodium is mixed by 3: 1: 1 mass ratio, by pH value of solution to regulation to 11, then solution temperature is adjusted to 75 DEG C
Afterwards, add 110Kg carries out reaction 6h with the mixture of TBAB and 1- chloro-2-hydroxypropyl-trimethyl ammonium chlorides, reacts
After the completion of solution is cooled down, be then added to device temperature for 180 DEG C, outlet temperature is to be done in 75 DEG C of spray drying device
Dry spraying, you can the loose powdered ceramic additive of black is obtained, wherein the dry powder rate of recovery after spray drying is 95.8%.
Embodiment 7
A kind of composite biomass base is modified the method for preparing ceramic additive, and it is comprised the following steps：
(1) percolate that 315Kg solid contents are 23% is concentrated into liquid and 220Kg with industrial tapioca and industry jade
Rice starch is carried out after ultrasonic wave mixes by the starch mixture that 1: 1 mass ratio is mixed into, in adding it to reactor,
And the catalyst that 1.4Kg mixes 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, carries out lasting stirring reaction 5h；
(2) toward sequentially adding 19Kg benzoic acid, 28Kg phenol, 61Kg in the solution after the completion of above-mentioned reaction with glutaraldehyde and
Aldehyde compound that metaformaldehyde in mass ratio 1: 1 is mixed, 65Kg are mixed with the concentrated sulfuric acid and sodium sulfite by 1: 1 mass ratio
The sulfonating agent and 60.6Kg water for closing, and system temperature is adjusted to 70 DEG C, react 9h；
(3) 3: 1 mass ratio is pressed with NaOH, sodium carbonate toward addition 65Kg in the solution after the completion of step (2) reaction
The pH adjusting agent for mixing, by pH value of solution to regulation to 9, then solution temperature is adjusted to after 85 DEG C, adds 165Kg with 1-
The mixture of chloro-2-hydroxypropyl-trimethyl ammonium chloride and dodecyl dimethyl hydroxyethyl ammonium nitrate carries out reaction 5h, has reacted
Solution is cooled down after, is then added to device temperature for 210 DEG C, outlet temperature is to be dried in 86 DEG C of spray drying device
Spraying, you can the loose powdered ceramic additive of black is obtained, wherein the dry powder rate of recovery after spray drying is 96.5%.
Embodiment 8
A kind of composite biomass base is modified the method for preparing ceramic additive, and it is comprised the following steps：
(1) percolate that 550Kg solid contents are 45% is concentrated into liquid and 150Kg with industrial potato starch and industry jade
Rice starch is carried out after ultrasonic wave mixes by the starch mixture that 1: 1 mass ratio is mixed into, in adding it to reactor,
And add the catalyst that 1.1Kg mixes with ferrous sulfate, ferric sulfate by 1: 1 mass ratio, and by system temperature adjust to
85 DEG C, pH value is adjusted to 9.5, carries out lasting stirring reaction 5h；
(2) toward sequentially adding 23Kg benzoic acid, 21Kg phenol, 50Kg in the solution after the completion of above-mentioned reaction with methacrylaldehyde and
Aldehyde compound that paraformaldehyde in mass ratio 1: 1 is mixed, 40Kg are mixed with the concentrated sulfuric acid and ammonium persulfate by 1: 1 mass ratio
The sulfonating agent and 29.9Kg water for closing, and system temperature is adjusted to 70 DEG C, react 6h；
(3) 2: 1 quality is pressed with NaOH, sodium acid carbonate toward addition 75Kg in the solution after the completion of step (2) reaction
Than the pH adjusting agent for mixing, by pH value of solution to regulation to 10, then solution temperature is adjusted to after 90 DEG C, add 60Kg 12
Alkyl dimethyl hydroxyethyl ammonium nitrate carries out reaction 6h, cools down solution after the completion of reaction, and it is 320 to be then added to device temperature
DEG C, outlet temperature is to be dried spraying in 92 DEG C of spray drying device, you can the loose powdered ceramic of black is obtained and adds
Plus agent, wherein the dry powder rate of recovery after spray drying is 97.8%.
Performance test
By ceramic additive obtained in embodiment 1~8 and conventional in the market additive (sodium tripolyphosphate and water glass
Glass in mass ratio 5: 2 mixes) contrasted, it is added into being used in the ceramic batch of formula as shown in the table：
| ZhangZhou clay | 45% |
| Kaolin | 30% |
| Montmorillonite | 15% |
| Silica flour | 10% |
Obtained comparative sample and embodiment 1~8 are carried out to carry out performance test comparison, gained knot using obtained sample
Fruit is as follows：
Note：
1. the delivery time use of ceramic sauce applies -4 glasss of measure, is represented with the time used by 100 milliliters of slurries of outflow；
2. the test of green compact rupture strength is with reference to the world parts of GBT3810.4-2006 the 4th：The modulus of rupture and breakdown strength
Determine.
The above is embodiments of the invention, for the ordinary skill in the art, religion of the invention
Lead, without departing from the principles and spirit of the present invention all impartial changes done according to scope of the present invention patent, repair
Change, replace and modification, should all belong to covering scope of the invention.
Claims (10)
1. a kind of composite biomass base is modified the method for preparing ceramic additive, it is characterised in that：Liquid is concentrated with percolate
It is raw material, after adding starch, passes sequentially through alkalization, sulfonation and quaterisation and ceramic additive is obtained.
2. a kind of composite biomass base according to claim 1 is modified the method for preparing ceramic additive, it is characterised in that：
It specifically includes following steps：
（1）Percolate is concentrated into liquid and starch carries out after ultrasonic wave mixes, adding catalyst, and system temperature is adjusted
To 65~95 DEG C, pH value is adjusted to 9~12 section, then carries out lasting 2~6h of stirring reaction；
（2）Benzoic acid, phenol, aldehyde compound, sulfonating agent and water are sequentially added toward the solution after the completion of above-mentioned reaction, and will
System temperature is adjusted to 70~100 DEG C, reacts 1.5~9h；
（3）Toward step（2）PH adjusting agent is added in solution after the completion of reaction, by pH value of solution to adjusting to 9~12, then by solution
Temperature adjustment cools down solution after the completion of reaction to after 70~100 DEG C, adding the quaternizing agent to carry out 3~6h of reaction, adds
Spraying is dried in spray drying device, you can the loose powdered ceramic additive of black is obtained.
3. a kind of composite biomass base according to claim 2 is modified the method for preparing ceramic additive, it is characterised in that：
The addO-on therapy and mass fraction of each step are as follows：
Percolate concentrates liquid 35%~55%；
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%.
4. a kind of composite biomass base according to claim 2 crosses 3 is modified the method for preparing ceramic additive, and its feature exists
In：Described percolate concentration liquid be percolate stoste by the concentrate after biochemical film concentration, it is described
The solid content of percolate concentration liquid is 10%~45%.
5. a kind of composite biomass base according to Claims 2 or 3 is modified the method for preparing ceramic additive, and its feature exists
In：Described starch is at least in Corn Starch, industrial potato starch, industrial wheat starch, industrial tapioca
Plant and mix.
6. a kind of composite biomass base according to Claims 2 or 3 is modified the method for preparing ceramic additive, and its feature exists
In：Described pH adjusting agent is NaOH, potassium carbonate, sodium carbonate, sodium citrate, potassium citrate, sodium sesquicarbonate, citric acid
At least one in one sodium, citric acid, lactic acid, tartaric acid, malic acid, metatartaric acid, sulfuric acid is mixed.
7. a kind of composite biomass base according to Claims 2 or 3 is modified the method for preparing ceramic additive, and its feature exists
In：Described catalyst is zinc sulfate, zinc nitrate, copper sulphate, copper nitrate, ferric nitrate, ferrous sulfate, ferrous nitrate, sulfuric acid Asia
At least one in iron ammonium, nickel sulfate is mixed.
8. a kind of composite biomass base according to Claims 2 or 3 is modified the method for preparing ceramic additive, and its feature exists
In：Described aldehyde compound is that at least one in formaldehyde, acetaldehyde, glutaraldehyde, methacrylaldehyde, metaformaldehyde, paraformaldehyde is mixed
Conjunction is formed；Described quaternizing agent is chloro- 2 hydroxypropyl-trimethyl ammonium chlorides of 1-, dodecyl benzyl dimethyl ammonium chloride, ten
At least one in eight alkyl dimethyl hydroxyethyl ammonium nitrates, hydrogen sulfate TBuA, TBAB is mixed.
9. a kind of composite biomass base according to Claims 2 or 3 is modified the method for preparing ceramic additive, and its feature exists
In：Described quaternizing agent is chloro- 2 hydroxypropyl-trimethyl ammonium chlorides of 1-, dodecyl benzyl dimethyl ammonium chloride, octadecane
At least one in base dimethyl hydroxy ethyl ammonium nitrate, hydrogen sulfate TBuA, TBAB is mixed.
10. a kind of composite biomass base according to Claims 2 or 3 is modified the method for preparing ceramic additive, its feature
It is：The device temperature of described spray drying device is 140~350 DEG C, and outlet temperature is 70~95 DEG C, through dry after spraying
The powder rate of recovery is more 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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