CN110156358A - A kind of bunt gypsum turn brilliant exciting agent, preparation method and application - Google Patents
A kind of bunt gypsum turn brilliant exciting agent, preparation method and application Download PDFInfo
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- CN110156358A CN110156358A CN201910285317.7A CN201910285317A CN110156358A CN 110156358 A CN110156358 A CN 110156358A CN 201910285317 A CN201910285317 A CN 201910285317A CN 110156358 A CN110156358 A CN 110156358A
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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
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
- C04B11/024—Ingredients added before, or during, the calcining process, e.g. calcination modifiers
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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
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
- C04B11/028—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained
- C04B11/032—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained for the wet process, e.g. dehydrating in solution or under saturated vapour conditions, i.e. to obtain alpha-hemihydrate
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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
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
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Abstract
The present invention relates to a kind of bunt gypsums to turn brilliant exciting agent, which turns the preparation method of brilliant exciting agent, for the grafted maleic anhydride triethanolamine ester on acidified starch；Specifically includes the following steps: acidified starch；Synthesis of maleic anhydride triethanolamine ester；Will be starch-grafted to maleic anhydride triethanolamine ester after acidolysis using semidry method, bunt gypsum is prepared and turns brilliant exciting agent.And relates to the use of the exciting agent and realize that bunt gypsum turns brilliant method.Exciting agent in the present invention can one-step method bunt gypsum Direct Hydrothermal is turned brilliant is α type-high-strength semi-hydrated gypsum, the competitive advantage of bunt gypsum series of products is greatly improved, realizes scale, the high-valued utilization of resources of by-product bunt gypsum.
Description
Technical field
Turn brilliant exciting agent, preparation method the present invention relates to a kind of exciting agent more particularly to a kind of bunt gypsum and utilizes this turn
The method that brilliant exciting agent realizes bunt gypsum crystal transfer.
Background technique
Bunt gypsum is a kind of salt industry by-product waste residue.2,600,000 tons of the annual by-product bunt gypsum in China, ranks first in the world.For
Valuable natural resources are saved in the utilization of resources for promoting the by-product gypsums such as bunt gypsum.
Since bunt gypsum granularity is small, intensity is low, it is easy absorption water and impurity, saliferous rate is high, if adding directly as cement
Agent or building material product can reduce the intensity of cement, and can cause to corrode to reinforcing bar to a certain extent, influence building safety.Cause
This, bunt gypsum cannot be used directly as cement retarder, can not directly prepare building gypsum, the cost of resource utilization
It is more much higher than desulfurized gypsum and ardealite these two types by-product gypsum with difficulty.And a large amount of bunt gypsums by salinization enterprise year in year out
It is deposited in plant area or discharges in violation of rules and regulations, not only cause land resource waste, stacking cost soaring, but also cause centainly to coastal environment
Pollution and destruction, become salt making enterprises and government's facing, urgent problem to be solved.
The primary raw material of plastering is semi-hydrated gypsum, and semi-hydrated gypsum is divided into alpha semi-hydrated gypsum and beta-type semi-hydrated gypsum again.
The difference of process conditions, causes alpha semi-hydrated gypsum intensity to be far longer than beta-type semi-hydrated gypsum when because of semi-hydrated gypsum formation.When dry
It is dehydrated under dry environment, forms beta-type semi-hydrated gypsum, and in the environment of non-dry, it will form α type-semi-hydrated gypsum.Half water stone of β type
The crystallinity of its crystal grain of cream is poor, more loose, tiny and irregular, and form is mostly sheet, is on a small quantity lamellar crystal form.α type-
Its crystallization of semi-hydrated gypsum is more complete, coarse and finer and close, is very different its specific surface area than beta-type semi-hydrated gypsum.Half water of α type
High-intensitive cementitious material is formed after gypsum crystal hardening, possesses that antistatic erosion medium resistance effect is strong, surface is smooth, at high temperature
The features such as volume change is small, compared with β type type semi-hydrated gypsum, water requirement is few, and has higher compactness and intensity.
The document of external industry by-product gypsum resource utilization is more, but because using vacuum salt production purification techniques, secondary
The amount for producing bunt gypsum is less, and bunt gypsum utilization of resources report is few.
The brilliant process of hydro-thermal excitation turn of common gypsum is simple, and bunt gypsum, which turns brilliant exciting agent, can be divided into inorganic salts and organic acid
(salt) two class, wherein inorganic salts include aluminum sulfate, ferric sulfate and 12 hydrazine aluminum sulfate potassium (alum) etc., organic acid (salt) class
It includes anhydrous sodium acetate, sodium citrate, tartaric acid etc. that bunt gypsum, which turns brilliant exciting agent,.
Sodium chloride content is affected to crystalline substance is turned, and when salt content is more than 5%, traditional salt gypsum rotating crystal exciting agent turns brilliant effect
Greatly decline, as salt content increases, grain aspect ratio is become larger, and coarse-grain is reduced, and fine grain increases, half water stone of β type in product
Cream content increases, and causes plastering water requirement big, final strength is lower.And bunt gypsum is sandwiched as salt & chemical industry by-product
Salinity is more, is not easy to remove, therefore bunt gypsum turns brilliant larger using difficulty, needs to develop high special of, tolerance level strong to salt adaptation
Turn brilliant exciting agent with special efficacy bunt gypsum.
Comprehensive domestic and international progress, bunt gypsum resource utilization have two, saliferous rate height and partial size is small, intensity
Low problem.For problem containing villaumite, two kinds of means of WATER-WASHING METHOD and recrystallization can be used, because bunt gypsum partial size is small, specific surface area
Greatly, villaumite is easily sandwiched, directly goes the ability of removing chloride limited by method for washing；Recrystallization method can be significant by bunt gypsum partial size
Increase, specific surface area decline, effectively reduce gypsum raw material to the absorption of villaumite and sandwich ability, reduces the residual content of salt.
Patent CN101475328A describes a kind of gypsum rotating crystal exciting agent and answering in bunt gypsum production building gypsum
With bunt gypsum being recrystallized by hydro-thermal method as dihydrate gypsum, then dihydrate gypsum product is become half water stone of β type by roasting
Cream is used as common gypsum building materials.This method is effectively reduced by recrystallization reduces bunt gypsum salt content, improves dihydrate gypsum crystalline substance
Shape is conducive to improve product quality, but process route is relatively long, and energy consumption is larger, and final products are common for common gypsum building materials
Beta-type semi-hydrated gypsum, economic value added is relatively low, and competitive advantage is unobvious.
Patent CN101734871A, which is described, to carry out purification process to desulfurized gypsum, turns brilliant reaction, crystallographic orientation, washing
The method of the alpha semi-hydrated gypsum crystal of short cylinder is grown into after separation, dry grinding process step；Patent CN103011641A is situated between
The method to have continued using chlor-alkali liquid waste processing ardealite reaction preparation high activity alpha semi-hydrated gypsum cementitious material.Desulfurized gypsum and
The crystalline form of ardealite is more regular compared with bunt gypsum, crystal grain is thicker, and villaumite is free of in impurity, and hydro-thermal turns brilliant rule and the natural gypsum
It is more similar；But bunt gypsum, because of self-characteristic, turning brilliant by one-step method hydro-thermal is that there are still larger for high-strength semi-hydrated gypsum for α type-
Difficulty needs to carry out correlative study, solves this technical problem.
It is α type-high-strength semi-hydrated gypsum process route that bunt gypsum one-step method Direct Hydrothermal, which turns brilliant, and bunt gypsum system can be greatly improved
The competitive advantage of column product realizes scale, the high-valued utilization of resources of by-product bunt gypsum, is conducive to environmental protection and economic effect
The two-win of benefit.
Summary of the invention
Maleic anhydride and triethanolamine itself, which can be used as, turns brilliant organic crystal modifier in gypsum hydro-thermal, and volume is generally
0.1%~0.2%, and both organic crystal modifiers price itself is higher, causes application cost higher.But with most of organic turn of crystalline substances
Agent is the same, and maleic anhydride and triethanolamine turn brilliant effect decline obviously under the conditions of high saliferous, and need to significantly improve volume can just take
Preferable effect is obtained, so that application cost is significantly soaring.Starch is as renewable resource, and from a wealth of sources, cheap, reserves are rich
Richness has natural macromolecular structure.Maleic anhydride triethanolamine carboxylate is grafted on starch polymer chain, and formation is regular to be had
The three-dimensional comb shaped structure of sequence can reduce gypsum crystallization process to the embedding effect of crystal modifier, improve the effective of crystal modifier in solution
Concentration, and the molecular structure of this 3 D stereo, improve the activity of maleic acid and triethanolamine, further improve and turn crystalline substance
Efficiency, while the dosage of maleic anhydride and triethanolamine is reduced, reduce production cost.Furthermore starch molecule contains largely
Hydroxyl, and hydroxyl can in gypsum calcium ion generate complexing, be conducive to maleic anhydride and triethanolamine realization cooperate with
Effect realizes composite synergistic, improves crystal modifier to the tolerance level of salt.Hydro-thermal is turned brilliant and is realized using one-step method, has technique letter
Just, the short advantage of market process.The high-strength building gypsum of barren rock α type can largely be cut down by this method.Alpha semi-hydrated gypsum partial size compared with
Slightly, crystalline form is regular, reduces absorption and embedding effect of the gypsum to salt, greatly reduces the content of salt in product.
The technical solution used in the present invention are as follows: a kind of bunt gypsum turns the preparation method of brilliant exciting agent, on acidified starch
Grafted maleic anhydride triethanolamine ester；Specifically includes the following steps:
S01 acidified starch；
S02 synthesis of maleic anhydride triethanolamine ester；
S03 will be starch-grafted to maleic anhydride triethanolamine ester after acidolysis using semidry method, and bunt gypsum is prepared and turns brilliant sharp
Send out agent.
Further, the acidified starch detailed process are as follows:
Starch is added water to be modulated into the starch milk that starch quality content is 40% ~ 50% by a；
The concentrated sulfuric acid is added into the starch milk and reacts by b, and the quality of the concentrated sulfuric acid is starch quality 1% ~ 5%, reaction
Temperature is 20 ~ 60 DEG C, and the reaction time is 1 ~ 2h；
C is after reaction filtered by vacuum reaction product, washed, dry after save.
Further, maleic anhydride triethanolamine ester synthesis process are as follows: triethanolamine and excessive Malaysia are added into container
Acid anhydrides, and the catalyst for being catalyzed the maleic anhydride and triethanolamine reaction is added, catalysis reaction 5h-6h, reaction temperature is 75 ~
80 DEG C to get maleic anhydride triethanolamine ester and maleic anhydride mixture.
Further, the step S03 specifically:
A prepares the aqueous solution of bleeding agent, and the starch after acidolysis is added in the aqueous solution of Xiang Suoshu bleeding agent obtains mixed liquor one；
Maleic anhydride triethanolamine ester and maleic anhydride mixture are added into mixed liquor one and is uniformly mixed by b obtains mixture
Two；
Mixture two is put into 70 DEG C ~ 90 DEG C baking ovens by c, and after reacting 2 ~ 4h, drying and grinding product obtains gypsum rotating crystal excitation
Agent.
Further, the mass ratio of the maleic anhydride and the triethanolamine is 0.02 ~ 0.04:0.015 ~ 0.03.
Further, the bleeding agent is sodium carbonate.
Further, the mass ratio of 0.02 ~ 0.04:1 of mass ratio of maleic anhydride and starch, triethanolamine and starch
0.015~0.03:1。
Further, the starch is cornstarch, potato starch, tapioca or wheaten starch.
Further, the concentrated sulfuric acid concentration is 98%.
Further, the catalyst is p-methyl benzenesulfonic acid.
Further, starch acidolysis reaction is carried out at 20 ~ 60 DEG C, and the heating reaction time is 1 ~ 2h.
Further, the additional amount of bleeding agent aqueous solution is the 5% ~ 10% of dry weight of starch.
Turn brilliant the invention further relates to bunt gypsum made from a kind of preparation method for turning brilliant exciting agent according to above-mentioned bunt gypsum to swash
Send out agent.
Brilliant exciting agent is turned using above-mentioned bunt gypsum, bunt gypsum is turned into brilliant method, included the following steps
A by bunt gypsum add water be configured to mass fraction be 15%~40% slurries and by the slurries be placed in reactor tank；
The brilliant exciting agent of bunt gypsum turn is added into the reactor tank and carries out turning brilliant reaction by b, obtains alpha semi-hydrated gypsum；
The alpha semi-hydrated gypsum slurries for completing crystallization are separated by solid-liquid separation by c, and the solid obtained to separation of solid and liquid is washed and dried
Pure alpha semi-hydrated gypsum crystal is obtained, the washing is done to be washed using 90 DEG C or more of saturation calcium sulfate hydrothermal solution
Dry temperature is 120~170 DEG C.
Further, it is the 0.1 ~ 1% of bunt gypsum weight that the bunt gypsum, which turns the volume of brilliant exciting agent,.
Beneficial effect caused by the present invention includes: the present invention by research and development preparation new salts gypsum rotating crystal exciting agent, is opened
Hair turns crystal technique, and it is alpha type high-strength gypsum that bunt gypsum one-step method Direct Hydrothermal can be made, which to turn brilliant,.Due to Malaysia when wherein using semidry method
Acid anhydrides is suitably excessive, can be catalyzed autoreactivity, excessive maleic anhydride continues and Starch formation graft, and maleic anhydride is inherently
It is that gypsum bunt gypsum turns brilliant exciting agent, is further promoted and turn brilliant efficiency, self-catalysis effect avoids waste material waste.And starch
With environmentally protective, it is convenient to draw materials, the feature cheap, processing is easy.Direct one-step method directly obtains alpha semi-hydrated gypsum province
Excess step is removed, energy consumption, simple flow are reduced.
Bunt gypsum is handled by using the brilliant exciting agent of the high dedicated special efficacy bunt gypsum of, tolerance level strong to salt adaptation turn,
A turn multiple recycled for brilliant mother liquor may be implemented.Turn brilliant mother liquor in recycled because salt accumulation salinity can gradually rise
Height, common crystal modifier are low to salt tolerance level, and turning brilliant efficiency can be remarkably decreased in recycled because salinity increases, it is difficult to realize
The multiple recycled for turning brilliant mother liquor causes the waste of crystal modifier and wastewater discharge to increase.
For product α type-high-strength semi-hydrated gypsum since draw ratio is small, partial size is thick, crystalline form is regular, advantageously reduces the double team of salt,
The content of salt in product is reduced, then is saturated the washing filtering of gypsum solution by heat, the remaining rate of salt can be effectively reduced.Because
Salt has corrosion function to reinforced concrete, can accelerate reinforcement corrosion.Be conducive to gypsum product to assist in steel and concrete structure
With in use, reducing the negative effect to project durability.
Main characteristics are as follows:
(1) crystal modifier prepared has salt tolerant, advantage efficiently, inexpensive.Starch is at low cost, and special three-dimensional is formed after grafting
Comb shaped molecular structure, improves the activity of maleic acid and triethanolamine, and the hydroxyl that starch is rich in is assisted by calcium ion complexing
With turn brilliant effect of service hoisting maleic acid and triethanolamine, realizes composite synergistic, promote tolerance of the crystal modifier to gypsum saliferous
Degree, while the dosage of maleic acid and triethanolamine is effectively reduced.
(2) this method can largely cut down bunt gypsum waste residue, save a large amount of soils, decrease bunt gypsum waste residue bring ring
Border pollution problem.It is advantageously implemented the recycling and higher value application of high saliferous condition bunt gypsum by-product.
(3) crystal modifier prepared by the present invention, which is mainly used in, turns the brilliant preparation high-strength building gypsum of α type for bunt gypsum waste residue,
Adapt to 25% high saliferous rate, when production is recyclable to apply, and reduces discharge of wastewater, reduces production cost.
(4) can realize that bunt gypsum one-step method Direct Hydrothermal turns brilliant by using crystal modifier of the present invention is the high-strength stone of α type
Cream, method is easy, shortens process, reduces energy consumption, improves and turns brilliant efficiency.
(5) the high-strength building gypsum of preparation α type of this law preparation, intensity is high, applied widely, is conducive to promote building materials of gypsum
Quality expands building materials of gypsum application field.Using by-product gypsum as raw material, production cost is greatly reduced, there is significant economic effect
Benefit and competitive advantage.Higher by the hydro-thermal rotating crystal method preparation high-strength semi-hydrated gypsum purity of α type, partial size is thick, crystalline form is regular, saliferous
It measures that low, water requirement is small, intensity is high, advantageously reduces the chlorine salt corrosion to Reinforcing Steel Bar In Reinforced Concrete Structure.
Detailed description of the invention
Fig. 1 blank group crystal morphology；
2 crystal morphology of Fig. 2 embodiment；
3 crystal morphology of Fig. 3 embodiment；
5 crystal morphology of Fig. 4 embodiment；
Fig. 5 crystal modifier infrared spectrogram.
Specific embodiment
Further details of explanation is done to the present invention in the following with reference to the drawings and specific embodiments, it should be appreciated that this
The protection scope of invention is not limited by the specific implementation.
Embodiment 1
By technical grade common corn starch 50g, water 75g is added to be modulated into starch milk, 98% concentrated sulfuric acid 2g is added, then water-bath adds
To 50 DEG C, 2h stops heating heat later, is down to room temperature and does not neutralize, and retains remaining sulfuric acid, dry using vacuum filtration, washing
After acidified starch can be obtained, and store at low temperature.
2.5g maleic anhydride and 1.5g triethanolamine are added into four-hole bottle, and 0.1g p-methyl benzenesulfonic acid is added, slowly rises
For temperature to 80 DEG C, reaction time 6h, cooling can obtain maleic anhydride triethanolamine ester and maleic anhydride mixture.
0.2g sodium carbonate is dissolved in 5g water, acidified starch is added and is heated to 60 DEG C of constant temperature 0.5h after mixing evenly, then
It is sufficiently mixed after maleic anhydride triethanolamine ester and maleic anhydride mixture is added, stirs evenly, synthesized using semidry method, is put into
3h is reacted in 80 DEG C of baking ovens, rear drying and grinding is cooled to room temperature and obtains the brilliant exciting agent of bunt gypsum turn.
Add water to be configured to 40% slurries bunt gypsum under normal pressure to enter pressure-resistant kettle, 1% salt stone of bunt gypsum quality is added
Cream turns brilliant exciting agent, closed pressure resistant kettle, and heating slurries carry out turning brilliant reaction, conversion reaction time 8h to 140 DEG C；It will complete to crystallize
Alpha semi-hydrated gypsum slurries be separated by solid-liquid separation, washed with 90 DEG C of saturation calcium sulfate hydrothermal solution, pure half water of α type that will be obtained
Gypsum crystal is dried in 130 DEG C of conditions, carries out grinding according to application fineness after drying to get pure half water stone of α type is arrived
Cream powder.
Embodiment 2
By technical grade common corn starch 40g, water 75g is added to be modulated into starch milk, 98% concentrated sulfuric acid 1g is added, then water-bath adds
To 45 DEG C, 1.5h stops heating heat later, is down to room temperature and does not neutralize, and retains remaining sulfuric acid, using vacuum filtration, washing, does
Acidified starch can be obtained after dry, and store at low temperature.2g maleic anhydride and 1.7g triethanolamine are added into four-hole bottle, and
0.1g p-methyl benzenesulfonic acid is added, is to slowly warm up to 82 DEG C, reaction time 5h, cooling can obtain maleic anhydride triethanolamine ester and horse
Carry out acid anhydride mixture.0.2g sodium carbonate is dissolved in 7g water, acidified starch is added and is heated to 65 DEG C of constant temperature after mixing evenly
0.5h is sufficiently mixed after adding maleic anhydride triethanolamine ester and maleic anhydride mixture, stirs evenly, closed using semidry method
At being put into 80 DEG C of baking ovens and react 2.5h, be cooled to room temperature rear drying and grinding and obtain bunt gypsum and turn brilliant exciting agent.
Add water to be configured to 30% slurries in gypsum under normal pressure and enter pressure-resistant kettle, the bunt gypsum for being added 0.4% turns brilliant excitation
Agent, closed pressure resistant kettle, heating slurries carry out turning brilliant reaction, conversion reaction time 8h to 145 DEG C；It will complete half water of α type of crystallization
Gypsum slurries are separated by solid-liquid separation, and are washed with 90 DEG C of saturation calcium sulfate hydrothermal solution, obtained pure alpha semi-hydrated gypsum crystal is existed
130 DEG C of conditions are dried, and carry out grinding according to application fineness after drying to get pure alpha semi-hydrated gypsum powder is arrived.
Embodiment 3
By technical grade common corn starch 45g, water 70g is added to be modulated into starch milk, 98% concentrated sulfuric acid 1.5g, then water-bath is added
50 DEG C are heated to, 2h stops heating later, is down to room temperature and does not neutralize, and retains remaining sulfuric acid, using vacuum filtration, washing, does
Acidified starch can be obtained after dry, and store at low temperature.2.5g maleic anhydride and 1.5g triethanolamine are added into four-hole bottle,
And 0.1g p-methyl benzenesulfonic acid is added, be to slowly warm up to 80 DEG C, reaction time 6h, cooling can obtain maleic anhydride triethanolamine ester and
Maleic anhydride mixture.0.2g sodium carbonate is dissolved in 5g water, acidified starch is added and is heated to 70 DEG C of constant temperature after mixing evenly
0.5h is sufficiently mixed after adding maleic anhydride triethanolamine ester and maleic anhydride mixture, stirs evenly, closed using semidry method
At being put into 80 DEG C of baking ovens and react 3h, be cooled to room temperature rear drying and grinding and obtain bunt gypsum and turn brilliant exciting agent.
Add water to be configured to 25% slurries in gypsum under normal pressure and enter pressure-resistant kettle, the bunt gypsum for being added 0.5% turns brilliant excitation
Agent, closed pressure resistant kettle, heating slurries carry out turning brilliant reaction, conversion reaction time 8h to 140 DEG C；It will complete half water of α type of crystallization
Gypsum slurries are separated by solid-liquid separation, and are washed with 90 DEG C of saturation calcium sulfate hydrothermal solution, obtained pure alpha semi-hydrated gypsum crystal is existed
130 DEG C of conditions are dried, and carry out grinding according to application fineness after drying to get pure alpha semi-hydrated gypsum powder is arrived.
Embodiment 4
By technical grade common corn starch 50g, water 75g is added to be modulated into starch milk, 98% concentrated sulfuric acid 2g is added, then water-bath adds
Heat is to 55 DEG C, 2.5h stops heating later, is down to room temperature and does not neutralize, and retains remaining sulfuric acid, using vacuum filtration, washing, does
Acidified starch can be obtained after dry, and store at low temperature.2.5g maleic anhydride and 2g triethanolamine are added into four-hole bottle, and
0.1g p-methyl benzenesulfonic acid is added, is to slowly warm up to 80 DEG C, reaction time 6h, cooling can obtain maleic anhydride triethanolamine ester and horse
Carry out acid anhydride mixture.0.2g sodium carbonate is dissolved in 8g water, acidified starch is added and is heated to 60 DEG C of constant temperature 1h after mixing evenly,
It is sufficiently mixed after adding maleic anhydride triethanolamine ester and maleic anhydride mixture, stirs evenly, synthesized using semidry method, put
Enter in 80 DEG C of baking ovens and react 3h, is cooled to room temperature rear drying and grinding and obtains the brilliant exciting agent of bunt gypsum turn.
Add water to be configured to 15% slurries in gypsum under normal pressure and enter pressure-resistant kettle, the bunt gypsum for being added 0.1% turns brilliant excitation
Agent, closed pressure resistant kettle, heating slurries carry out turning brilliant reaction, conversion reaction time 5h to 140 DEG C；It will complete half water of α type of crystallization
Gypsum slurries are separated by solid-liquid separation, and are washed with 95 DEG C of saturation calcium sulfate hydrothermal solution, obtained pure alpha semi-hydrated gypsum crystal is existed
130 DEG C of conditions are dried, and carry out grinding according to application fineness after drying to get pure alpha semi-hydrated gypsum powder is arrived.
Embodiment 5
By technical grade common corn starch 55g, water 75g is added to be modulated into starch milk, 98% concentrated sulfuric acid 2g is added, then water-bath adds
To 50 DEG C, 2h stops heating heat later, is down to room temperature and does not neutralize, and retains remaining sulfuric acid, dry using vacuum filtration, washing
After acidified starch can be obtained, and store at low temperature.2.5g maleic anhydride and 2.2g triethanolamine are added into four-hole bottle, and
0.1g p-methyl benzenesulfonic acid is added, is to slowly warm up to 80 DEG C, reaction time 6h, cooling can obtain maleic anhydride triethanolamine ester and horse
Carry out acid anhydride mixture.0.1g sodium carbonate is dissolved in 5g water, acidified starch is added and is heated to 60 DEG C of constant temperature after mixing evenly
0.5h is sufficiently mixed after adding maleic anhydride triethanolamine ester and maleic anhydride mixture, stirs evenly, closed using semidry method
At being put into 80 DEG C of baking ovens and react 3h, be cooled to room temperature rear drying and grinding and obtain bunt gypsum and turn brilliant exciting agent.
Add water to be configured to 30% slurries in gypsum under normal pressure and enter pressure-resistant kettle, the bunt gypsum for being added 0.5% turns brilliant excitation
Agent, closed pressure resistant kettle, heating slurries carry out turning brilliant reaction, conversion reaction time 6h to 140 DEG C；It will complete half water of α type of crystallization
Gypsum slurries are separated by solid-liquid separation, and are washed with 93 DEG C of saturation calcium sulfate hydrothermal solution, obtained pure alpha semi-hydrated gypsum crystal is existed
130 DEG C of conditions are dried, and carry out grinding according to application fineness after drying to get pure alpha semi-hydrated gypsum powder is arrived.
Embodiment 6
By technical grade common corn starch 50g, water 80g is added to be modulated into starch milk, 98% concentrated sulfuric acid 2g is added, then water-bath adds
To 50 DEG C, 2h stops heating heat later, is down to room temperature and does not neutralize, and retains remaining sulfuric acid, dry using vacuum filtration, washing
After acidified starch can be obtained, and store at low temperature.2.5g maleic anhydride and 1.5g triethanolamine are added into four-hole bottle, and
0.1g p-methyl benzenesulfonic acid is added, is to slowly warm up to 85 DEG C, reaction time 5h, cooling can obtain maleic anhydride triethanolamine ester and horse
Carry out acid anhydride mixture.0.2g sodium carbonate is dissolved in 5g water, acidified starch is added and is heated to 60 DEG C of constant temperature after mixing evenly
0.5h is sufficiently mixed after adding maleic anhydride triethanolamine ester and maleic anhydride mixture, stirs evenly, closed using semidry method
At being put into 80 DEG C of baking ovens and react 3h, be cooled to room temperature rear drying and grinding and obtain bunt gypsum and turn brilliant exciting agent.
Add water to be configured to 35% slurries addition pressure-resistant kettle in gypsum under normal pressure, the 0.5% brilliant excitation of bunt gypsum turn is added
Agent, closed pressure resistant kettle, heating slurries carry out turning brilliant reaction, conversion reaction time 8h to 142 DEG C；It will complete half water of α type of crystallization
Gypsum slurries are separated by solid-liquid separation, and are washed with 85 DEG C of saturation calcium sulfate hydrothermal solution, obtained pure alpha semi-hydrated gypsum crystal is existed
130 DEG C of conditions are dried, and carry out grinding according to application fineness after drying to get pure alpha semi-hydrated gypsum powder is arrived.
This gypsum rotating crystal exciting agent is particularly suitable for the saliferous gypsum rotating crystal that sodium chloride content is 0-15% and handles.
Performance test
It will be seen from figure 1 that the crystal structure degree for not mixing the brilliant exciting agent of bunt gypsum turn is poor, more loose, tiny and irregular,
Form is mostly sheet, is on a small quantity lamellar crystal form, predominantly beta-type semi-hydrated gypsum.Fig. 2, Fig. 3 and Fig. 4 all alpha semi-hydrated gypsums,
Crystallization is all than more complete, coarse and fine and close, and draw ratio is small, and crystalline form is regular, and specific surface area is noticeably greater than Fig. 1.
1 semi-hydrated gypsum performance test of table
| Group | Blank | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Consumptive use of water normal consistence | 48% | 35% | 36% | 32% | 30% | 37% | 40% |
| Flexural strength/MPa | 2 | 11.2 | 11.7 | 12.5 | 11.3 | 12.8 | 12.0 |
| Compression strength/MPa | 8 | 35.2 | 42.3 | 39.4 | 41.2 | 38.5 | 40.3 |
Flexural strength has the wet flexural strength of 2h and 40 DEG C of dry flexural strengths.The wet flexural strength of 2h refers to land plaster from being put into water
In count, after 2h on anti-folding instrument the intensity tested；40 DEG C of dry flexural strengths are samples in 40 ± 4 DEG C of electric heating forced air dryings
The flexural strength tested after drying in case to constant weight.The general 2.7Mpa or more of wet flexural strength of β land plaster, dry anti-folding are strong
Spend general 6Mpa or more；The general 4Mpa or more of wet flexural strength of alpha gypsum powder, the dry general 7Mpa or more of flexural strength.
In ceramic industry, the flexural strength of land plaster is usually detected, compression strength does not detect generally.The 2h of land plaster is wet anti-
Compressive Strength is generally 6Mpa or more, does compression strength 12Mpa or more.
Flexural strength detection method:
1. the quality for calculating manufactured size as land plaster used in gypsum strip 3 of 40 × 40 × 60 ㎜ and water (presses land plaster
Normal consistency or mass production plaster-water ratio example), and weigh respectively.First water is injected in 2000ml container, by land plaster in 30s
It is inside equably sprinkled into water, stands 30s, then quickly stir 1min, calcium plaster is injected in mould immediately, by one end of mould
It is fallen again after lifting about 10mm with hand, so vibration 5 times, to exclude bubble.When reaching initial set, excessive slurry is scraped off with scraper, to
It is demoulded after final set.
Detection method of compression strength:
1. being made into the test block of the ㎜ × 40 of 40 ㎜ × 40 ㎜ using the half sample after the test of above-mentioned flexural strength.
It finds that bunt gypsum turns brilliant exciting agent and can debase the standard consistency water consumption by table 1, and promotes compression strength.
Infrared spectrogram is as shown in Figure 5.As shown in Figure 5,3420 cm of wave number-1Strong absworption peak, be in starch-OH stretches
Contracting vibration peak, 2920cm-1Corresponding C-H characteristic peak, 1160cm-1、1060cm-1, 1010m-1 series of peaks be starch in C-C, C-
O stretching vibration peak and C-OH bending vibration characteristic peak, fingerprint region 550cm-1、575cm-1Series of peaks is then that starch backbone absorbs
Peak.1730cm-1The characteristic absorption peak at place is spy caused by the symmetric and anti-symmetric stretching vibration of C=O key on maleic acid anhydro ring
Levy absorption peak, 1640cm-1Place is C=C vibration absorption peak of maleic anhydride, 1410cm-1Place is the CH of triethanolamine2Bending vibration
Absorption peak shows that maleic anhydride and triethanolamine are successfully grafted on starch molecular chain.
The above is only a preferred embodiment of the present invention, and the present invention is not limited in the content of embodiment.For in this field
Technical staff for, can have various change and change within the scope of technical solution of the present invention, made any variation and
Change, within that scope of the present invention.
Claims (10)
1. the preparation method that a kind of bunt gypsum turns brilliant exciting agent, it is characterised in that: three second of grafted maleic anhydride on acidified starch
Alkanolamine ester；Specifically includes the following steps:
S01 acidified starch；
S02 prepares maleic anhydride triethanolamine ester and maleic anhydride mixture；
S03 will be starch-grafted to maleic anhydride triethanolamine ester after acidolysis using semidry method, and bunt gypsum is prepared and turns brilliant sharp
Send out agent.
2. the preparation method that bunt gypsum according to claim 1 turns brilliant exciting agent, it is characterised in that: the acidified starch tool
Body process are as follows:
Starch is added water to be modulated into the starch milk that starch quality content is 40% ~ 50% by a；
The concentrated sulfuric acid is added into the starch milk and reacts by b, and the quality of the concentrated sulfuric acid is starch quality 1% ~ 5%, reaction
Temperature is 20 ~ 60 DEG C, and the reaction time is 1 ~ 2h；
C is after reaction filtered by vacuum reaction product, washed, dry after save.
3. the preparation method that bunt gypsum according to claim 1 turns brilliant exciting agent, it is characterised in that: three ethyl alcohol of maleic anhydride
Amine ester and maleic anhydride mixture preparation process are as follows: triethanolamine and excessive maleic anhydride are added into container, and catalysis is added
The catalyst of the maleic anhydride and triethanolamine reaction, catalysis reaction 5h-6h, reaction temperature is 75 ~ 80 DEG C to get maleic acid
Acid anhydride triethanolamine ester and maleic anhydride mixture.
4. the preparation method that bunt gypsum according to claim 1 turns brilliant exciting agent, it is characterised in that: the step S03 tool
Body are as follows:
A prepares the aqueous solution of bleeding agent, and the starch after acidolysis is added in the aqueous solution of Xiang Suoshu bleeding agent obtains mixed liquor one；
Maleic anhydride triethanolamine ester and maleic anhydride mixture are added into mixed liquor one and is uniformly mixed by b obtains mixture
Two；
Mixture two is put into 70 DEG C ~ 90 DEG C baking ovens by c, and after reacting 2 ~ 4h, drying and grinding product obtains gypsum rotating crystal excitation
Agent.
5. the preparation method that bunt gypsum according to claim 3 turns brilliant exciting agent, it is characterised in that: the maleic anhydride with
The mass ratio of the triethanolamine is 0.02 ~ 0.04:0.015 ~ 0.03.
6. the preparation method that bunt gypsum according to claim 4 turns brilliant exciting agent, it is characterised in that: the bleeding agent is carbon
Sour sodium.
7. the preparation method that bunt gypsum according to claim 1 turns brilliant exciting agent, it is characterised in that: bleeding agent aqueous solution
Additional amount is the 5% ~ 10% of dry weight of starch.
8. a kind of any one of -7 bunt gypsums according to claim 1 turn bunt gypsum made from the preparation method of brilliant exciting agent and turn crystalline substance
Exciting agent.
9. a kind of turn the brilliant exciting agent method that bunt gypsum turn is brilliant using bunt gypsum according to any one of claims 8, it is characterised in that: packet
Include following steps
A by bunt gypsum add water be configured to mass fraction be 15%~40% slurries and by the slurries be placed in reactor tank；
The brilliant exciting agent of bunt gypsum turn is added into the reactor tank and carries out turning brilliant reaction by b, obtains alpha semi-hydrated gypsum；
The alpha semi-hydrated gypsum slurries for completing crystallization are separated by solid-liquid separation by c, and the solid obtained to separation of solid and liquid is washed and dried
Obtain pure alpha semi-hydrated gypsum crystal, the washing to be washed using saturation calcium sulphate soln, drying temperature is 120~
170℃。
10. bunt gypsum according to claim 9 turns brilliant method, it is characterised in that: the bunt gypsum turns brilliant exciting agent
Volume is the 0.1 ~ 1% of bunt gypsum weight.
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| CN113149513A (en) * | 2021-05-12 | 2021-07-23 | 太原科技大学 | Reinforced crystal transformation auxiliary agent for calcining building gypsum and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU695983A1 (en) * | 1972-10-02 | 1979-11-05 | Институт общей и неорганической химии АН Армянской ССР | Method of preparing gypsum binder |
| JPS5738355A (en) * | 1980-08-19 | 1982-03-03 | Tomoji Tanaka | Hardness adjustment for molding byproduct gypsum obtained on hydrogen fluoride manufacture |
| CN101058488A (en) * | 2007-04-10 | 2007-10-24 | 山东金信新型建材有限公司 | Process for producing alpha gypsum powder by liquid phase method |
| CN101475328A (en) * | 2009-01-20 | 2009-07-08 | 天津科技大学 | Gypsum rotating crystal excitant and use for producing construction gypsum from marine gypsum |
| CN105174760A (en) * | 2015-09-18 | 2015-12-23 | 金正大生态工程集团股份有限公司 | Method for preparing alpha semi-hydrated gypsum from dihydrate gypsum |
| CN107936127A (en) * | 2017-11-27 | 2018-04-20 | 河海大学 | A kind of corrosion inhibition type starch base water-reducing agent and preparation method thereof |
| CN107936126A (en) * | 2017-11-27 | 2018-04-20 | 河海大学 | One kind resistance rust type starch base water-reducing agent and preparation method thereof |
-
2019
- 2019-04-10 CN CN201910285317.7A patent/CN110156358B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU695983A1 (en) * | 1972-10-02 | 1979-11-05 | Институт общей и неорганической химии АН Армянской ССР | Method of preparing gypsum binder |
| JPS5738355A (en) * | 1980-08-19 | 1982-03-03 | Tomoji Tanaka | Hardness adjustment for molding byproduct gypsum obtained on hydrogen fluoride manufacture |
| CN101058488A (en) * | 2007-04-10 | 2007-10-24 | 山东金信新型建材有限公司 | Process for producing alpha gypsum powder by liquid phase method |
| CN101475328A (en) * | 2009-01-20 | 2009-07-08 | 天津科技大学 | Gypsum rotating crystal excitant and use for producing construction gypsum from marine gypsum |
| CN105174760A (en) * | 2015-09-18 | 2015-12-23 | 金正大生态工程集团股份有限公司 | Method for preparing alpha semi-hydrated gypsum from dihydrate gypsum |
| CN107936127A (en) * | 2017-11-27 | 2018-04-20 | 河海大学 | A kind of corrosion inhibition type starch base water-reducing agent and preparation method thereof |
| CN107936126A (en) * | 2017-11-27 | 2018-04-20 | 河海大学 | One kind resistance rust type starch base water-reducing agent and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113149513A (en) * | 2021-05-12 | 2021-07-23 | 太原科技大学 | Reinforced crystal transformation auxiliary agent for calcining building gypsum and preparation method thereof |
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