CN108439618A - A kind of coal gasification buck scale preventative and preparation method thereof - Google Patents
A kind of coal gasification buck scale preventative and preparation method thereof Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
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Abstract
The present invention provides a kind of preparation methods of coal gasification buck scale preventative, including：Natural polymer is oxidized, sulfonation obtains sulfonation modifying product；The amination modifying product that the sulfonation modifying product amination of 10wt%~20wt% is obtained；The sulfonation modifying product of 40wt%~60wt% is obtained into copolymerization product under the action of initiator with the copolyreaction of one or more of acrylic acid and maleic acid；The sulfonation modifying product, amination modifying product and copolymerization product of 20wt%~50wt% are mixed, coal gasification buck scale preventative is obtained.The present invention obtains amination modifying product that sulfonation modifying product and sulfonation modifying product amination obtain by natural polymer is oxidized, sulfonation and copolymerization product mixes, synergistic effect, collectively as coal gasification buck scale preventative, high molecular polymer is modified by above-mentioned oxidative degradation, sulfonation, selective amination and graft copolymerization etc., finally obtained coal gasification buck scale preventative scale inhibition performance is high.
Description
Technical field
The present invention relates to Treatment of Industrial Water technical fields, more particularly, to a kind of coal gasification buck scale preventative and its preparation side
Method.
Background technology
The water system of coal gasification apparatus is to ensure one of the important link of gasification furnace long-period stable operation.Gasification installation water
The pressure of system be 4.0~8.0MPa, temperature be 150~250 DEG C, while buck be high rigidity, high alkalinity, width pH ranges it is easy
Fouling type water quality, in the operational process of device often along with Incrustation of pipe, the problem of blocking, especially gasification furnace shock chamber,
The foulings such as Heisui River pipeline, evaporation hot-water tower, water scrubber, grey water- to-water heat exchanger are serious.It is normal to solve coal gasification apparatus buck scale problems
The method used has the dirt dispersion agent of excellent scale-inhibiting properties to be added.
Currently, the dirt dispersion agent of domestic a few well-known medicament producers of family is successfully answered in the water system of coal gasification apparatus
With, and realize the safe and stable and long-term operation of coal gasification apparatus water system.But suitable for the resistance to of coal gasification apparatus
High alkalinity, high rigidity, high temperature and pressure dirt dispersion agent be mainly Compositional type medicament, such as patent of invention CN103086524B " one
Kind High-efficiency grey water dispersant " mainly uses acrylic acid -2- acrylamide-2-methyl propane sulfonics, 2- phosphate -1,2,4- tricarboxylic acids
Five kinds of monomer composite reagents such as butane, aminotrimethylenephosphonic acid, hydroxy ethylene diphosphonic acid, hydrolyzed polymaleic anhydride are made；Hair
A kind of bright patent CN1254442C " dirt dispersion agent and its manufacturing method for coal gas of high temperature wash-water system " mainly uses
The three of hydrolysis of polymaleic anhydride, acrylic compounds bipolymer, acrylic acid-alkyl acrylate-unsaturated monomer containing sulfonic acid group
Several monomer composite reagents such as membered copolymer are made.But the compounding based on organic phosphine series, polycarboxylic acid monomer medicament
Type coal gasification Grey water antiscale dispersion agent, gradually faces that the raw material production costs such as acrylic acid and maleic acid are excessively high, and compound drug is to height
The problems such as coal for gasification bad adaptability of grey high calcium, gasification system operation only January when certain coal gasification apparatus fouling of the country is serious,
The 95% of internal diameter of the pipeline is by fouling Severe blockage.
Therefore, the production method for how improving coal gasification buck scale preventative improves economy, the adaptability of buck scale preventative
And environmental requirement, it is current problem in the urgent need to address.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation side of coal gasification buck scale preventative
Method, coal gasification buck scale preventative scale inhibition performance prepared by the present invention are high.
The present invention provides a kind of preparation methods of coal gasification buck scale preventative, including：
A) natural polymer is oxidized, sulfonation obtains sulfonation modifying product；
B) the amination modifying product for obtaining the sulfonation modifying product amination of 10wt%~20wt%；
By the sulfonation modifying product of 40wt%~60wt% under the action of initiator with one in acrylic acid and maleic acid
Kind or several copolyreaction, obtain copolymerization product；
C) the sulfonation modifying product of 20wt%~50wt%, amination modifying product and copolymerization product are mixed, obtain coal gas
Change buck scale preventative.
Preferably, the natural polymer is selected from one or more of lignin, humic acid and tannin.
Preferably, the amination modifying product is that the sulfonation modifying product amination of 12wt%~20wt% obtains；It is described total
Poly- product be 45wt%~55wt% sulfonation modifying product under the action of initiator with one kind in acrylic acid and maleic acid
Or several graft copolymerizations obtain；The coal gasification buck scale preventative be by the sulfonation modifying product of 25wt%~45wt%,
Amination modifying product and copolymerization product are mixed to get.
Preferably, step A) it is described oxidation be specially：Natural polymer is adjusted into pH value to 8.0~9.0, is mixed with oxidant
It closes, 1.5~2.0h of oxidation reaction at 80 DEG C~90 DEG C obtains oxidative breakdown product；The oxidant is selected from Feton reagents, height
One or more of potassium manganate and nitric acid.
Preferably, step A) sulfonation is specially：Oxidative breakdown product is mixed with sulfonating agent, it is anti-at 100~150 DEG C
2.0~3.0h is answered, sulfonation modifying product is obtained；The sulfonating agent is in sodium sulfite, sodium hydrogensulfite and sodium thiosulfate
One or more.
Preferably, amination described in step B is specially：The sulfonation modifying product of 10wt%~20wt% is mixed with aminating agent
Close 130~160 DEG C of 0.5~1h of reaction；It is mixed again with aldehyde compound, adjusts and reacted at most 7.0~9.0,50~60 DEG C of pH
0.5~1.0h, then mixed with dimethylamine, 0.5~1.0h is reacted at 40~50 DEG C, obtains amination modifying product；The amination examination
Agent is one or more of concentrated ammonia liquor, dimethylamine and branched alkyl amine；The aldehyde compound is formaldehyde.
Preferably, graft copolymerization described in step B is specially：
By the sulfonation modifying product of 40wt%~60wt% under the action of initiator with one in acrylic acid and maleic acid
Kind or several 30~40 DEG C of 2~3h of graft copolymerization, obtain copolymerization product；The initiator is Feton reagents.
Preferably, one or more of acrylic acid and maleic acid and the mass ratio of sulfonation modifying product described in step B are
(3~5):1；The mass ratio of the initiator and sulfonation modifying product is 1:7~8.
Preferably, in the mixture of the acrylic acid and maleic acid, the mass ratio of acrylic acid and maleic acid is (40~60)：
(40~60).
The present invention provides a kind of coal gasification buck scale preventatives, by the preparation method described in above-mentioned technical proposal any one
It is prepared.
Compared with prior art, the present invention provides a kind of preparation methods of coal gasification buck scale preventative, including：A) natural
Polymer is oxidized, sulfonation obtains sulfonation modifying product；B) the sulfonation modifying product amination of 10wt%~20wt% is obtained
Amination modifying product；By the sulfonation modifying product of 40wt%~60wt% under the action of initiator in acrylic acid and maleic acid
One or more of copolyreaction, obtain copolymerization product；C) the sulfonation modifying product of 20wt%~50wt%, amination modifying are produced
Object and copolymerization product mixing, obtain coal gasification buck scale preventative.The present invention obtains sulphur by natural polymer is oxidized, sulfonation
Change amination modifying product that modified product and sulfonation modifying product amination obtain and copolymerization product mixes, synergistic effect, jointly
As coal gasification buck scale preventative, i.e., by above-mentioned oxidative degradation, sulfonation, selective amination and graft copolymerization etc. to polyphosphazene polymer
Object modification is closed, finally obtained coal gasification buck scale preventative scale inhibition performance is high；Economic simultaneously, environmental protection.
Specific implementation mode
The present invention provides a kind of coal gasification buck scale preventative and preparation method thereof, those skilled in the art can use for reference this
Literary content is suitably modified technological parameter realization.In particular, it should be pointed out that all similar substitutions and modifications are to art technology
It is it will be apparent that they shall fall within the protection scope of the present invention for personnel.The present invention method and application by compared with
Good embodiment is described, related personnel obviously can not depart from the content of present invention, in spirit and scope to methods herein
It is modified or suitably changes and combine with application, to realize and apply the technology of the present invention.
The present invention provides a kind of preparation methods of coal gasification buck scale preventative, including：
A) natural polymer is oxidized, sulfonation obtains sulfonation modifying product；
B) the amination modifying product for obtaining the sulfonation modifying product amination of 10wt%~20wt%；
By the sulfonation modifying product of 40wt%~60wt% under the action of initiator with one in acrylic acid and maleic acid
Kind or several copolyreaction, obtain copolymerization product；
C) the sulfonation modifying product of 20wt%~50wt%, amination modifying product and copolymerization product are mixed, obtain coal gas
Change buck scale preventative.
The preparation method of coal gasification buck scale preventative provided by the invention first aoxidizes natural polymer.
Natural polymer of the present invention includes but not limited to one or more of lignin, humic acid and tannin.
Oxidation of the present invention is specially：Natural polymer is adjusted into pH value to 8.0~9.0, is mixed with oxidant, 80 DEG C
1.5~2.0h of oxidation reaction, obtains oxidative breakdown product at~90 DEG C；The oxidant be selected from Feton reagents, potassium permanganate and
One or more of nitric acid.
The wherein natural polymer adjusts pH value to 8.0~9.0 and is specially：By natural polymer and sodium carbonate or hydrogen-oxygen
Change sodium solution mixing, obtain mixed reactant, adjusts pH value to 8.0~9.0.Wherein, the quality of the mixture reactant point
Number is 20~30%.
It after obtaining mixed reactant, is mixed with oxidant, 1.5~2.0h of oxidation reaction at 80 DEG C~90 DEG C is aoxidized
Catabolite.
Wherein, the oxidant is preferably selected from one or more of Feton reagents, potassium permanganate and nitric acid.
The mass ratio of the oxidant and reactant is preferably (1~1.5):1；More preferably (1.1~1.4):1.Institute
The temperature for stating oxidation reaction is preferably 82 DEG C~88 DEG C；The reaction time is preferably 1.6~1.8h.
Natural polymer oxidative degradation of the present invention, transformation obtain small molecule, can increase active function groups group carboxyl, hydroxyl
The content of base, phenolic hydroxyl group, and then improve the dispersion activity of natural polymers.
After oxidation, oxidative breakdown product sulfonation is obtained into sulfonation modifying product.
In the present invention, the sulfonation is specially：Oxidative breakdown product is mixed with sulfonating agent, is reacted at 100~150 DEG C
2.0~3.0h obtains sulfonation modifying product；The sulfonating agent is in sodium sulfite, sodium hydrogensulfite and sodium thiosulfate
It is one or more of.
Wherein, the mass ratio of the oxidative breakdown product and sulfonating agent is preferably (1.5~2.0):1；More preferably (1.6
~1.8):1.
The temperature of the sulfonating reaction is preferably 110~140 DEG C；The reaction time is preferably 2.1~2.8h.
The reaction preferably carries out in a kettle.
The present invention is by sulfonation modifying, by introducing the anion base that one or more hydrophilies are strong, hydration shell is thicker
Group -- sulfonic group increases the activity of ring molecule, make the lignin, humic acid or tannin of small molecule have it is preferably water-soluble and
Dispersibility.
In the present invention, it is preferred to which the sulfonation modifying product amination of 10wt%~20wt% is obtained amination modifying product；More
It is preferred that the sulfonation modifying product amination of 12wt%~20wt% is obtained amination modifying product.
According to the present invention, the amination is preferably specially：The sulfonation modifying product of 10wt%~20wt% and ammonification are tried
Agent mixes 130~160 DEG C of 0.5~1h of reaction；It mixes, adjusts at most 7.0~9.0,50~60 DEG C of pH with aldehyde compound again
0.5~1.0h is reacted, then is mixed with dimethylamine, 0.5~1.0h is reacted at 40~50 DEG C, obtains amination modifying product；The amine
Change reagent is one or more of concentrated ammonia liquor, dimethylamine and branched alkyl amine；The aldehyde compound is formaldehyde.
Sulfonation modifying product is mixed 130~160 DEG C with aminating agent first and reacts 0.5~1h.Wherein, the amination examination
Agent is one or more of concentrated ammonia liquor, dimethylamine and branched alkyl amine；Preferably concentrated ammonia liquor or dimethylamine.
The mass ratio of sulfonation modifying product and aminating agent of the present invention is preferably 2~3:1；More preferably 2.5:1.Institute
It is preferably 140~150 DEG C to state reaction temperature；The reaction time is preferably 0.6~0.9h.Present invention reaction further includes stirring,
The present invention to its without limit, it is well known to those skilled in the art.
It is then mixed with aldehyde compound, adjusts and react 0.5~1.0h at most 7.0~9.0,50~60 DEG C of pH.Institute
It is preferably formaldehyde to state aldehyde compound.
Wherein, the mass ratio of the reactant and aldehyde compound is preferably 0.9~1.0:1；More preferably 0.9:1.This
It invents the adjusting pH most 7.0~9.0 and preferably adjusts pH most 7.0~9.0 using sodium carbonate.The reaction temperature is preferred
It is 52~58 DEG C；The reaction time is preferably 0.6~0.9h.
It is then mixed with dimethylamine, 0.5~1.0h is reacted at 40~50 DEG C, obtains amination modifying product.
Wherein, the addition of dimethylamine is preferably the 80%~95% of formaldehyde quality；More preferably 85%~90%；It is optimal
It is selected as 90%.The reaction preferably carries out in a kettle, and the present invention is to the reaction kettle without restriction, people in the art
Known to member；The reaction temperature is preferably 42~48 DEG C；The reaction time is preferably 0.6~0.9h.
Partly sulfonated modified product is carried out amination modifying, active hydrogen by the present invention using Mannich (Mannich) reactions
Atom is replaced by amine methyl, and amine methyl is introduced in the structure of the lignin of small molecule, humic acid or tannin, improves natural polymerization
The complex performance of object, scale-inhibiting properties increase.
By the sulfonation modifying product of 40wt%~60wt% under the action of initiator with one in acrylic acid and maleic acid
Kind or several copolyreaction, obtain copolymerization product.
It is currently preferred, by the sulfonation modifying product of 45wt%~55wt% under the action of initiator with acrylic acid and
One or more of maleic acid graft copolymerization obtains copolymerization product.
In the present invention, the graft copolymerization is preferably specially：
By the sulfonation modifying product of 40wt%~60wt% under the action of initiator with one in acrylic acid and maleic acid
Kind or several 30~40 DEG C of 2~3h of graft copolymerization, obtain copolymerization product；The initiator is Feton reagents.
The mass ratio of one or more of acrylic acid and maleic acid of the present invention and above-mentioned partly sulfonated modified product
Preferably (3~5):1, more preferably 4:1；The initiator is preferably slowly added to initiator, and initiator is Feton reagents,
Mass ratio with reactant is preferably 1:7~8, more preferably 1:7.It is reacted in reaction kettle；The reaction temperature is preferably 32
~38 DEG C；The reaction time is preferably 2.2~2.8h.
In the mixture of acrylic acid and maleic acid of the present invention, the mass ratio of acrylic acid and maleic acid is (40~60)：
(40~60).
In the present invention, by the sulfonation modifying product of above-mentioned part by the initiation of initiator, with acrylic acid, Malaysia
Graft copolymerization occurs for or mixtures thereof acid, and the modification of partial selective improves complexing and the dispersion performance of natural polymer, in turn
Improve scale-inhibiting properties.
Coal gasification buck scale preventative of the present invention preferably changes the sulfonation modifying product of 25wt%~45wt%, amination
Property product and copolymerization product are mixed to get.
The present invention is by sulfonation modifying product, sulfonation amination modified product, graft copolymer, according to the water quality of coal gasification buck
Characteristic selects above-mentioned specific ratio, is mixed, acted synergistically, and is made a kind of and novel is suitable for coal gasification buck
Non-phosphate environment-friendly type, high temperature resistant, the resistance to high-alkali dirt dispersion agent of system.
So design, through above-mentioned chemical modification, so that it may be given birth to using natural polymers lignin, humic acid, tannin
Produce non-phosphate environment-friendly type, high temperature resistant, resistance to high-alkali dirt dispersion agent.
The present invention also provides a kind of coal gasification buck scale preventatives, by the preparation side described in above-mentioned technical proposal any one
Method is prepared.
The present invention provides a kind of preparation methods of coal gasification buck scale preventative, including：A) natural polymer is oxidized, sulphur
Change obtains sulfonation modifying product；B) the amination modifying product for obtaining the sulfonation modifying product amination of 10wt%~20wt%；It will
The sulfonation modifying product of 40wt%~60wt% is total with one or more of acrylic acid and maleic acid under the action of initiator
Poly- reaction, obtains copolymerization product；C) the sulfonation modifying product of 20wt%~50wt%, amination modifying product and copolymerization product are mixed
It closes, obtains coal gasification buck scale preventative.The present invention obtains sulfonation modifying product and sulphur by natural polymer is oxidized, sulfonation
Change the amination modifying product and copolymerization product mixing that modified product amination obtains, synergistic effect, collectively as coal gasification buck
Antisludging agent is modified high molecular polymer by above-mentioned oxidative degradation, sulfonation, selective amination and graft copolymerization etc., finally
Obtained coal gasification buck scale preventative scale inhibition performance is high；Economic simultaneously, environmental protection.
The coal gasification buck scale preventative that the present invention is prepared dosage preferably in 230-250 DEG C of high temperature, coal gasification buck
Under conditions of 50~80ppm, scale inhibition performance is 83~87%, and scale inhibition performance and dispersion effect are better than existing commercial Application medicament.The present invention
Non-phosphate environment-friendly type, high temperature resistant, the resistance to high-alkali dirt dispersion agent of chemic modified method preparation have raw material sources extensive, environmentally friendly without dirt
Dye, the advantage applied widely to different coal gasification bucks, ensure that high temperature, the scale inhibition under high-alkali gasification ash water environment and dispersion
Effect.
In order to further illustrate the present invention, with reference to embodiments to a kind of coal gasification buck scale preventative provided by the invention
And preparation method thereof be described in detail.
Embodiment 1
15% sodium carbonate liquor is added in lignin, forms mixed reactant, mass fraction 25% controls pH value
Between 8.0-9.0.It is slowly added to Feton reagent oxidation agent, the mass ratio with lignin is 1:1, it is warming up in reaction kettle
1.5h is reacted at 85 DEG C.15% sodium carbonate or sodium hydroxide solution is added, carries out neutralization reaction, reacts 10-20min, pH value
Between 7.0-8.0.The mass ratio that sodium sulfite and reactant are added in the oxidative breakdown product of lignin is 1：1.8, it stirs
It mixes uniformly, is warming up in reaction kettle at 120 DEG C and reacts 2.0h, sulfonation modifying product is made.
By 15% Sulphonation of Lignin modified product, concentrated ammonia liquor is added, the mass ratio with reactant is 1:2.5, stirring is equal
It is even, it is warming up in reaction kettle at 150 DEG C and reacts 0.5h.A certain amount of formaldehyde is added, the mass ratio with reactant is 1:
0.9, pH value is adjusted between 7.0-9.0 with sodium carbonate liquor, is warming up in reaction kettle at 50-60 DEG C and is reacted 1.0h, then
Dimethylamine is added, addition is formaldehyde quality 90%, is warming up in reaction kettle at 40-50 DEG C and reacts 3.0h, obtained amination changes
Property product.
By 50% Sulphonation of Lignin modified product, the mixture of+40% maleic acid of 60% acrylic acid is added, with reactant
Mass ratio be 4:1, while it being slowly added to initiator, initiator is Feton reagents, and the mass ratio with reactant is 1:7, anti-
It answers in kettle and reacts 3.0h at 30-40 DEG C, graft copolymer is made.
By above-mentioned three kinds of modified products：35% sulfonation modifying product, 15% sulfonation amination modified product, 50% sulphur
Change modified product and+40% maleic acid graft copolymer of 60% acrylic acid, mixed, a kind of novel antiscaling dispersion is made
Agent, in 230-250 DEG C of high temperature, coal gasification buck under conditions of dosage 50ppm, scale inhibition performance 83%, iron oxide solution it is saturating
Light rate is 48%., scale inhibition performance and dispersion effect are better than existing commercial Application medicament.
Embodiment 2
15% sodium hydroxide solution is added in humic acid, forms mixed reactant, mass fraction 30% controls PH
Value is between 8.0-9.0.It is slowly added to 5% potassium permanganate oxidant, the mass ratio with humic acid is 1.5:1, in reaction kettle
It is warming up at 85 DEG C and reacts 1.5h.15% sodium carbonate or sodium hydroxide solution is added, carries out neutralization reaction, reacts 10-
20min, pH value is between 7.0-8.0.The quality of sodium hydrogensulfite and reactant is added in the oxidative breakdown product of humic acid
Than being 1：1.8, it stirs evenly, is warming up in reaction kettle at 120 DEG C and reacts 2.0h, sulfonation modifying product is made.
By 20% humic acid sulfonation modifying product, concentrated ammonia liquor is added, the mass ratio with reactant is 1:2.5, stirring is equal
It is even, it is warming up in reaction kettle at 150 DEG C and reacts 0.5h.A certain amount of formaldehyde is added, the mass ratio with reactant is 1:
0.9, pH value is adjusted between 7.0-9.0 with sodium carbonate liquor, is warming up in reaction kettle at 50-60 DEG C and is reacted 1.0h, then
Dimethylamine is added, addition is formaldehyde quality 90%, is warming up in reaction kettle at 40-50 DEG C and reacts 3.0h, obtained amination changes
Property product.
By 50% humic acid sulfonation modifying product, the mixture of+50% maleic acid of 50% acrylic acid is added, with reactant
Mass ratio be 5:1, while it being slowly added to initiator, initiator is Feton reagents, and the mass ratio with reactant is 1:7, anti-
It answers in kettle and reacts 3.0h at 30-40 DEG C, graft copolymer is made.
By above-mentioned three kinds of modified products：30% sulfonation modifying product, 20% sulfonation amination modified product, 50% sulphur
Change modified product and+50% maleic acid graft copolymer of 50% acrylic acid, mixed, a kind of novel antiscaling dispersion is made
Agent, in 230-250 DEG C of high temperature, coal gasification buck under conditions of dosage 50ppm, scale inhibition performance 86%, iron oxide solution it is saturating
Light rate is 49%., scale inhibition performance and dispersion effect are better than existing commercial Application medicament.
Comparative example 1
15% sodium carbonate liquor is added in lignin, forms mixed reactant, mass fraction 25% controls pH value
Between 8.0-9.0.It is slowly added to Feton reagent oxidation agent, the mass ratio with lignin is 1:1, it is warming up in reaction kettle
1.5h is reacted at 85 DEG C.15% sodium carbonate or sodium hydroxide solution is added, carries out neutralization reaction, reacts 10-20min, pH value
Between 7.0-8.0.The mass ratio that sodium sulfite and reactant are added in the oxidative breakdown product of lignin is 1：1.8, it stirs
It mixes uniformly, is warming up in reaction kettle at 120 DEG C and reacts 2.0h, sulfonation modifying product is made.
By 8% Sulphonation of Lignin modified product, concentrated ammonia liquor is added, the mass ratio with reactant is 1:2.5, stirring is equal
It is even, it is warming up in reaction kettle at 150 DEG C and reacts 0.5h.A certain amount of formaldehyde is added, the mass ratio with reactant is 1:
0.9, pH value is adjusted between 7.0-9.0 with sodium carbonate liquor, is warming up in reaction kettle at 50-60 DEG C and is reacted 1.0h, then
Dimethylamine is added, addition is formaldehyde quality 90%, is warming up in reaction kettle at 40-50 DEG C and reacts 3.0h, obtained amination changes
Property product.
By 32% Sulphonation of Lignin modified product, the mixture of+40% maleic acid of 60% acrylic acid is added, with reactant
Mass ratio be 4:1, while it being slowly added to initiator, initiator is Feton reagents, and the mass ratio with reactant is 1:7, anti-
It answers in kettle and reacts 3.0h at 30-40 DEG C, graft copolymer is made.
By above-mentioned three kinds of modified products：60% sulfonation modifying product, 8% sulfonation amination modified product, 32% sulphur
Change modified product and+40% maleic acid graft copolymer of 60% acrylic acid, mixed, a kind of novel antiscaling dispersion is made
Agent, in 230-250 DEG C of high temperature, coal gasification buck under conditions of dosage 50ppm, scale inhibition performance 69%, iron oxide solution it is saturating
Light rate is 72%.
Comparative example 2
15% sodium carbonate liquor is added in lignin, forms mixed reactant, mass fraction 25% controls pH value
Between 8.0-9.0.It is slowly added to Feton reagent oxidation agent, the mass ratio with lignin is 1:1, it is warming up in reaction kettle
1.5h is reacted at 85 DEG C.15% sodium carbonate or sodium hydroxide solution is added, carries out neutralization reaction, reacts 10-20min, pH value
Between 7.0-8.0.The mass ratio that sodium sulfite and reactant are added in the oxidative breakdown product of lignin is 1：1.8, it stirs
It mixes uniformly, is warming up in reaction kettle at 120 DEG C and reacts 2.0h, sulfonation modifying product is made.
By 50% Sulphonation of Lignin modified product, the mixture of+40% maleic acid of 60% acrylic acid is added, with reactant
Mass ratio be 4:1, while it being slowly added to initiator, initiator is Feton reagents, and the mass ratio with reactant is 1:7, anti-
It answers in kettle and reacts 3.0h at 30-40 DEG C, graft copolymer is made.
By above two modified product：50% sulfonation modifying product, 50% sulfonation modifying product and 60% acrylic acid+
40% maleic acid graft copolymer, is mixed, and a kind of novel dirt dispersion agent is made, in 230-250 DEG C of high temperature, coal gasification
In buck under conditions of dosage 50ppm, the light transmittance of scale inhibition performance 76%, iron oxide solution is 65%.
Comparative example 3
15% sodium carbonate liquor is added in lignin, forms mixed reactant, mass fraction 25% controls pH value
Between 8.0-9.0.It is slowly added to Feton reagent oxidation agent, the mass ratio with lignin is 1:1, it is warming up in reaction kettle
1.5h is reacted at 85 DEG C.15% sodium carbonate or sodium hydroxide solution is added, carries out neutralization reaction, reacts 10-20min, pH value
Between 7.0-8.0.The mass ratio that sodium sulfite and reactant are added in the oxidative breakdown product of lignin is 1：1.8, it stirs
It mixes uniformly, is warming up in reaction kettle at 120 DEG C and reacts 2.0h, sulfonation modifying product is made.
By 50% Sulphonation of Lignin modified product, concentrated ammonia liquor is added, the mass ratio with reactant is 1:2.5, stirring is equal
It is even, it is warming up in reaction kettle at 150 DEG C and reacts 0.5h.A certain amount of formaldehyde is added, the mass ratio with reactant is 1:
0.9, pH value is adjusted between 7.0-9.0 with sodium carbonate liquor, is warming up in reaction kettle at 50-60 DEG C and is reacted 1.0h, then
Dimethylamine is added, addition is formaldehyde quality 90%, is warming up in reaction kettle at 40-50 DEG C and reacts 3.0h, obtained amination changes
Property product.
By above two modified product：50% sulfonation modifying product, 50% sulfonation amination modified product mixed,
A kind of novel dirt dispersion agent, in 230-250 DEG C of high temperature, coal gasification buck under conditions of dosage 50ppm, scale inhibition performance is made
It is 75%, the light transmittance of iron oxide solution is 58%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of coal gasification buck scale preventative, which is characterized in that including：
A) natural polymer is oxidized, sulfonation obtains sulfonation modifying product；
B) the amination modifying product for obtaining the sulfonation modifying product amination of 10wt%~20wt%；
By the sulfonation modifying product of 40wt%~60wt% under the action of initiator in acrylic acid and maleic acid one kind or
Several copolyreaction, obtain copolymerization product；
C) the sulfonation modifying product of 20wt%~50wt%, amination modifying product and copolymerization product are mixed, obtain coal gas ashing
Water antisludging agent.
2. preparation method according to claim 1, which is characterized in that the natural polymer is selected from lignin, humic acid
One or more of with tannin.
3. preparation method according to claim 1, which is characterized in that the amination modifying product is 12wt%~20wt%
Sulfonation modifying product amination obtain；Work of the sulfonation modifying product in initiator that the copolymerization product is 45wt%~55wt%
It is obtained with one or more of acrylic acid and maleic acid graft copolymerization with lower；The coal gasification buck scale preventative is will
Sulfonation modifying product, amination modifying product and the copolymerization product of 25wt%~45wt% is mixed to get.
4. preparation method according to claim 1, which is characterized in that step A) it is described oxidation be specially：By natural polymerization
Object adjusts pH value to 8.0~9.0, is mixed with oxidant, 1.5~2.0h of oxidation reaction at 80 DEG C~90 DEG C obtains oxidative degradation
Product；The oxidant is selected from one or more of Feton reagents, potassium permanganate and nitric acid.
5. preparation method according to claim 4, which is characterized in that step A) sulfonation is specially：By oxidative degradation
Product is mixed with sulfonating agent, and 2.0~3.0h is reacted at 100~150 DEG C, obtains sulfonation modifying product；The sulfonating agent is selected from Asia
One or more of sodium sulphate, sodium hydrogensulfite and sodium thiosulfate.
6. preparation method according to claim 1, which is characterized in that amination described in step B is specially：By 10wt%~
The sulfonation modifying product of 20wt% mixes 130~160 DEG C with aminating agent and reacts 0.5~1h；It mixes, adjusts with aldehyde compound again
It saves and reacts 0.5~1.0h at most 7.0~9.0,50~60 DEG C of pH, then mix with dimethylamine, reaction 0.5 at 40~50 DEG C~
1.0h obtains amination modifying product；The amination reagent is one or more of concentrated ammonia liquor, dimethylamine and branched alkyl amine；
The aldehyde compound is formaldehyde.
7. preparation method according to claim 1, which is characterized in that graft copolymerization is specially described in step B：
By the sulfonation modifying product of 40wt%~60wt% under the action of initiator in acrylic acid and maleic acid one kind or
Several 30~40 DEG C of 2~3h of graft copolymerization, obtain copolymerization product；The initiator is Feton reagents.
8. preparation method according to claim 7, which is characterized in that one kind in acrylic acid and maleic acid described in step B
Or several mass ratioes with sulfonation modifying product are (3~5):1；The mass ratio of the initiator and sulfonation modifying product is 1:7
~8.
9. preparation method according to claim 7, which is characterized in that in the mixture of the acrylic acid and maleic acid, third
The mass ratio of olefin(e) acid and maleic acid is (40~60)：(40~60).
10. a kind of coal gasification buck scale preventative, which is characterized in that by preparation method system as described in any one of claim 1 to 9
It is standby to obtain.
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