CN110023253A - Sodium salt scale preventive agent, sodium salt dirt prevention method, water-based viscosity reductant, water-based management method and water-based process for reducing viscosity - Google Patents
Sodium salt scale preventive agent, sodium salt dirt prevention method, water-based viscosity reductant, water-based management method and water-based process for reducing viscosity Download PDFInfo
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- CN110023253A CN110023253A CN201780070999.9A CN201780070999A CN110023253A CN 110023253 A CN110023253 A CN 110023253A CN 201780070999 A CN201780070999 A CN 201780070999A CN 110023253 A CN110023253 A CN 110023253A
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- sodium salt
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- 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
It provides: a method of preventing the generation of the scale in the water system containing a large amount of sodium ions.Sodium salt scale preventive agent of the invention includes at least to contain sulfosalicylic polymer using unsaturated sulfonic acid system monomer as monomer.The preferred 700g/mol or more of weight average molecular weight and 70000g/mol or less containing sulfosalicylic polymer.In the case that the summation for constituting the molal quantity of whole monomers containing sulfosalicylic polymer is set as 100 moles of %, molal quantity preferably 3 moles of % or more of the unsaturated sulfonic acid system monomer containing sulfosalicylic polymer are constituted.
Description
Technical field
The present invention relates to sodium salt scale preventive agent, sodium salt dirt prevention method, water-based viscosity reductant, water-based management method and water
The process for reducing viscosity of system.
Background technique
The substance for dissolving or suspending in water is precipitated, precipitates or accumulates and solidify in the surface of solids, and generates scale.Scale
Chemical substance it is different according to the water system of generation, for example, calcium carbonate, calcium sulfate, calcium sulfite, calcium phosphate, silicic acid
Calcium, magnesium silicate, magnesium hydroxide, trbasic zinc phosphate, zinc hydroxide, alkaline carbonic acid zinc etc..
Equipment, garbage burning factory, the steel dust water system of water system, such as boiler, cooling water system that scale industrially utilizes
A large amount of devices such as equipment, flue gas desulfurization equipment, seawater water desalination device in be attached to heat-transfer surface, piping, wall etc., cause to change
Heating rate reduces, the breakage of device, is pumped rising, flow-reduction, the reduction of output, the interruption of running operation, the waste of the energy
Etc. various obstacles.Scale especially high temperature, it is high-alkali under the conditions of be easy to happen, once occur when, removal be not easy to.Cause
This, it is expected that continuously preventing scale from adhering in the case where not stopping operation.
Such as in patent document 1, in kraft pulp manufacturing process, as the knot for being effectively prevented the inside generation for steaming solution kettle
The scale-deposit-preventing adherence method of dirty phenomenon, proposes following method: adding poly- Malaysia into the white liquor or black liquor for steaming solution kettle in supply
Acid or its salt.In addition, in patent document 2, as continuously prevent from being attached in the steaming solution kettle of kraft pulp manufacturing process, its week
The method of the scale of piping, the equipment on side etc. proposes following method: adding acrylic acid-clothing in steaming the digester liquor in solution kettle
Health acid copolymer or its salt.Similarly, in patent document 3, as continuously preventing the steaming for being attached to kraft pulp manufacturing process
The scale attachment inhibitor for solving the calcium salt dirt of interior kettle, the piping on its periphery, equipment etc. proposes one kind and contains maleic acid-propylene
The scale attachment inhibitor of acid -2- acrylamide-2-methyl propane sulfonic terpolymer.In turn, in patent document 4, as changing
The method that the formation of calcium salt dirt in good chemical paper sludging process inhibits, proposes following method: adding phosphonic acids in steaming solution kettle
Derivative salt.
However, according to the difference of chemical substance, the prevention method of scale, minimizing technology are different, therefore, it is impossible to by needle
Preventing agent or prevention method to the scale formed by specific chemical substance are diverted to the water for other chemical substances immediately
The preventing agent of dirt, needs the chemical substance research prevention method according to each scale.In addition, in recent years, due to industrial technology
It complicates, for water-based additive throughout a variety of, therefore, the chemical substance of scale also spreads a variety of, the prevention method of scale
Exploitation it is extremely difficult.
Thus, in kraft pulp manufacturing process, piece is steamed into the Black Liquor Concentration after solution with alkali, is used as fuel and returns alkali
It receives.With the concentration of black liquor, the viscosity of the black liquor rises, and therefore, in recent years, has carried out following operation extensively: will be used as visbreaking
The sodium sulphate of agent is added to black liquor (such as non-patent literature 1 and 2).Also scale is generated in such water system, thermal effect when concentration
Rate reduces, and therefore, can not be effectively concentrated sometimes.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Publication 2-53551 bulletin
Patent document 2: Japanese Unexamined Patent Publication 4-136286 bulletin
Patent document 3: No. 3194867 bulletins of Japanese Patent No.
Patent document 4: Japanese Unexamined Patent Application Publication 2004-532945 bulletin
Non-patent literature
Non-patent literature 1: pulp technology association magazine, volume 64, No. 6, the 659-663 pages
Non-patent literature 2: pulp technology association magazine, volume 61, No. 5, the 519-522 pages
Summary of the invention
Problems to be solved by the invention
The present invention is made in view of the above actual conditions, it is intended that providing: being prevented for example as after above-mentioned concentration
Black liquor it is such, the method for the generation of the scale in the water system containing a large amount of sodium ions.
The solution to the problem
The present inventor in order to solve the above problems, furthers investigate repeatedly, as a result, it has been found that: the scale generated in black liquor, which is originated from, to be made
For the sodium salt (sodium sulphate, sodium carbonate etc.) of the sodium sulphate of viscosity reductant；With, defined polymer is added in water system, so as to
The generation for preventing the scale from sodium ion, so far completes the present invention.Specifically, the present invention provides scheme below.
(1) the 1st invention of the invention is a kind of sodium salt scale preventive agent, it includes: at least it is with unsaturated sulfonic acid system monomer
Monomer contains sulfosalicylic polymer.
(2) the 2nd invention of the invention is a kind of sodium salt scale preventive agent, and in the 1st invention, the aforementioned weight containing sulfosalicylic polymer is equal
Molecular weight is 700g/mol or more and 70000g/mol or less.
(3) the 3rd invention of the invention is a kind of sodium salt scale preventive agent, in the 1st or the 2nd invention, is constituted aforementioned poly- containing sulfo group
In the case that the summation of the molal quantity of whole monomers of conjunction object is set as 100 moles of %, constitute aforementioned containing the aforementioned of sulfosalicylic polymer
The molal quantity of unsaturated sulfonic acid system monomer is 3 moles of % or more.
(4) the 4th invention of the invention is a kind of sodium salt scale preventive agent, in the 1st to any one of 3rd invention, aforementioned insatiable hunger
It is selected from vinyl sulfonic acid, allyl sulphonic acid, 2- acrylamide-2-methyl propane sulfonic, 3- allyloxy -2- with sulfonic acid system monomer
Hydroxyl -1- sulfonic acid, 2- Methacrylamide -2- methyl propane sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, acrylamide methviium
One or more of the alkali metal salts or ammonium salt of sulfonic acid and they.
(5) the 5th invention of the invention is a kind of sodium salt scale preventive agent, aforementioned to contain sulphur in the 1st to any one of 4th invention
Based polyalcohol is at least using unsaturated sulfonic acid system monomer and carboxylic serials monomer as the copolymer of monomer.
(6) the 6th invention of the invention is a kind of sodium salt scale preventive agent, and in the 5th invention, aforementioned unsaturated carboxylic acid system monomer is
Selected from by acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and their alkali metal salt, ammonium salt
One or more of group of composition.
(7) the 7th invention of the invention is a kind of sodium salt dirt prevention method, and the 1st to any one of 6th is added in water system
The sodium salt scale preventive agent of invention.
(8) the 8th invention of the invention is a kind of sodium salt dirt prevention method, in the 7th invention, with aforementioned sodium salt scale preventive agent
Concentration becomes 1mg/L or more and 1000mg/L mode below is added to water system.
(9) the 9th invention of the invention is a kind of sodium salt dirt prevention method, and in the 7th or the 8th invention, aforementioned water system includes 1 matter
Measure the sodium sulphate of % or more.
(10) the 10th invention of the invention is a kind of sodium salt dirt prevention method, aforementioned in the 7th to any one of 9th invention
Water system is the black liquor in kraft pulp manufacturing process.
(11) the 11st invention of the invention is a kind of water-based viscosity reductant, it includes: sodium sulphate；With at least with unsaturation
Sulfonic acid system monomer is monomer containing sulfosalicylic polymer.
(12) the 12nd invention of the invention is a kind of water-based management method comprising following process: in same water system,
The process for adding sodium sulphate and addition are at least using unsaturated sulfonic acid system monomer as the process containing sulfosalicylic polymer of monomer.
(13) the 13rd invention of the invention is a kind of water-based process for reducing viscosity comprising following process: in same water system,
The process for adding sodium sulphate and addition are at least using unsaturated sulfonic acid system monomer as the process containing sulfosalicylic polymer of monomer.
The effect of invention
According to the present invention it is possible to prevent the generation of the scale in the water system containing a large amount of sodium ions.
Detailed description of the invention
Fig. 1 is the composition schematic diagram of the production equipment of the paper pulp of one embodiment of the present invention.
Specific embodiment
Hereinafter, a specific embodiment of the invention is described in detail, but the present invention is not appointed by following implementation
What is limited, and can be suitable for being changed and being implemented within the scope of the purpose of the present invention.
1. sodium salt scale preventive agent > of <
Present embodiment, sodium salt scale preventive agent using the sulfo group that contains that unsaturated sulfonic acid system monomer is monomer comprising at least being polymerize
Object.Such sodium salt scale preventive agent is added in the water system containing a large amount of sodium ions, to can prevent from being originated from sodium in the water system
The generation of the sodium salt scale of ion.
[containing sulfosalicylic polymer]
Containing sulfosalicylic polymer at least using unsaturated sulfonic acid system monomer as monomer.Sulfo group and sodium ion containing sulfosalicylic polymer
Compatibility is high, can be kept with ionic condition.Thus, it is possible to prevent the generation of the sodium salt scale from sodium ion.
(unsaturated sulfonic acid system monomer)
Unsaturated sulfonic acid system monomer refers to there is the compound of sulfo group and polymerizable functional group.In one embodiment, insatiable hunger
And sulfonic acid system monomer for example can the key between α position carbon and β carbon with sulfo group and carbonyl and carbonyl carbon be unsaturated carbon
The compound of key.In addition, in an embodiment, as unsaturated sulfonic acid system monomer, can be used for example selected from vinyl sulfonic acid,
Allyl sulphonic acid, 2- acrylamide-2-methyl propane sulfonic, 3- allyloxy -2- hydroxyl -1- sulfonic acid, 2- Methacrylamide -2-
In methyl propane sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, acrylamide methviium sulfonic acid and their alkali metal salts or ammonium salt
1 kind or more.Wherein, as alkali metal salt, such as have sodium salt, sylvite, as ammonium salt, can be used ammonia, monomethylamine, dimethylamine,
The salt such as mono aminoethane, diethylamine.
In one embodiment, the summation for constituting the molal quantity of whole monomers containing sulfosalicylic polymer is set as 100 moles of %
In the case where, containing in sulfosalicylic polymer, unsaturated sulfonic acid system monomer molal quantity such as preferably 3 moles of % or more, more preferable 5
Mole % or more, further preferred 6 moles of % or more, particularly preferred 8 moles of % or more.The molal quantity of unsaturated sulfonic acid system monomer
More than required amount, so as to improve sodium salt scale generation prevent effect.But unsaturated sulfonic acid system monomer rubs
You can be lower than 3 moles of % by number.
In one embodiment, the summation for constituting the molal quantity of whole monomers containing sulfosalicylic polymer is set as 100 moles of %
In the case where, the molal quantity of unsaturated sulfonic acid system monomer can for example rub for 100 moles of % or less, 90 moles of % or less, 80
You are % or less, 70 moles of % or less, 60 moles of % or less, 50 moles of % or less, 40 moles of % or less, 30 moles of % or less, 20
Mole % or less, 10 moles of % or less.
(unsaturated carboxylic acid system monomer)
It can be at least with unsaturated sulfonic acid system monomer and unsaturated carboxylic acid system list containing sulfosalicylic polymer in one embodiment
Body is the polymer of monomer.
Unsaturated carboxylic acid system monomer refers to that the key between the α position carbon and β carbon of carboxylic acid is the compound of unsaturated carbon bond.
In one embodiment, as unsaturated carboxylic acid system monomer, can be used for example selected from by acrylic acid, methacrylic acid, maleic acid,
One or more of maleic anhydride, itaconic acid, itaconic anhydride and their alkali metal salt, the group of ammonium salt composition.Wherein, as alkali
Metal salt, such as have sodium salt, sylvite, as ammonium salt, the salt such as ammonia, monomethylamine, dimethylamine, mono aminoethane, diethylamine can be used.
(other monomers)
In one embodiment, containing in sulfosalicylic polymer, in the range of not damaging the effect of the purpose of the present invention, it can incite somebody to action
Constituent of the monomer as polymer other than above-mentioned unsaturated carboxylic acid system monomer and unsaturated sulfonic acid system monomer.
In one embodiment, as other monomers, for example, vinyl phosphonic acid, allylin, allyl
Alcohol, (methyl) acrylamide, N- alkyl (methyl) acrylamide, (methyl) acrylonitrile, vinyl acetate, styrene, isobutene
Deng.
In one embodiment, containing sulfosalicylic polymer the molal quantity that will constitute whole monomers containing sulfosalicylic polymer summation
In the case where being set as 100 moles of %, it can rub containing such as 95 moles of % or less, 90 moles of % or less, 80 moles of % or less, 70
You are % or less, 60 moles of % or less, 50 moles of % or less, 40 moles of % or less, 30 moles of % or less, 20 moles of % or less, 10
Mole % or less, 8 moles of % or less, 6 moles of % or less, 5 moles of % or less, 4 moles of % or less, 3 moles of % or less, 2 are rubbed
Your % or less, 1 mole of % or less, 0.5 mole of % or less, 0.2 mole of % or less, 0.1 mole of % or less, 0.05 mole of % with
Under, 0.02 mole of % or less, 0.01 mole of % other monomers below.
(weight average molecular weight (the M containing sulfosalicylic polymerw))
In one embodiment, the weight average molecular weight (M containing sulfosalicylic polymerw) for example preferred 200g/mol or more, more preferably
700g/mol or more, further preferred 1000g/mol or more, particularly preferred 2000g/mol or more.On the other hand, poly- containing sulfo group
Close the preferred 120000g/mol or less of weight average molecular weight, more preferable 70000g/mol or less, the further preferred 50000g/mol of object
Below, particularly preferably 14000g/mol or less.Wherein, weight average molecular weight can be lower than 200g/mol or more than 120000g/mol.
Weight average molecular weight containing sulfosalicylic polymer be required amount, so as to improve sodium salt scale generation prevent effect.In addition,
The weight average molecular weight of polymer with carboxyl is 120000 hereinafter, water-based caused by polymer so as to inhibit to add
Viscosity rises, and is easy operation." weight average molecular weight " refers to following value herein: using polyethylene glycol known to molecular weight as standard
Substance is found out by gel permeation chromatography.
(manufacturing method)
It as the manufacturing method containing sulfosalicylic polymer, is not particularly limited, in an embodiment, solution can be used for example
Polymerization, bulk polymerization etc. and manufacture.For containing sulfosalicylic polymer, the monomer as raw material be mostly it is water-soluble, under above situation,
The aqueous solution polymerization taken water as a solvent can be used for example.In aqueous solution polymerization, the water-soluble of 5~50 weight % of monomer is prepared
Liquid replaces atmosphere by non-active gas, is heated to 50~100 DEG C, water-soluble polymerization initiator added, so as to be gathered
It closes.As water-soluble polymerization initiator, for example, 4,4 '-azos bis- (4- cyanopentanoic acids), bis- (the 2- first of 2,2 '-azos
The third amidine of base) the persulfates series initiators, mistake such as azo initiators, ammonium persulfate, sodium peroxydisulfate, the potassium peroxydisulfate such as dihydrochloride
Peroxide series initiators such as hydrogen oxide, sodium metaperiodate etc..In addition, as needed, alcohols, phosphoric acid class etc. can be used as chain
Transfer agent.Under such circumstances, polymerization usually terminates in 3~6 hours, carries out natural cooling, so as to obtain containing sulfo group
The aqueous solution of polymer.
[other compositions]
In one embodiment, sodium salt scale preventive agent can be containing containing sulphur in the range of not damaging purpose of the present invention effect
Ingredient other than based polyalcohol.Such as sodium salt scale preventive agent can contain polyacrylic acid (salt), poly (salt) etc..
It in one embodiment, is applied in combination containing sulfosalicylic polymer and sodium sulphate, can also be used as viscosity reductant and use.One is real
It applies in mode, as viscosity reductant, can be formed comprising sodium sulphate and the above-mentioned preparation containing sulfosalicylic polymer.By using such
Viscosity reductant, so as to which it is high to reduce the viscosity such as the black liquor in kraft pulp manufacturing process in the case where not generating scale
Water-based viscosity or its rising can be inhibited.
2. sodium salt dirt prevention method > of <
The sodium salt dirt prevention method of present embodiment is to add the sodium salt dirt of above-mentioned sodium salt scale preventive agent in water system to prevent
Method.
Hold in the water system of sodium sulphate comprising high concentration (such as 1 mass % or more, 2 mass % or more, 3 mass % or more)
It is also easy to produce sodium salt scale.In such water system, above-mentioned sodium salt scale preventive agent is added in water system, so that the sodium salt scale preventive agent
Concentration become 1mg/L or more and 1000mg/L hereinafter, generation so as to prevent sodium salt scale.
In one embodiment, with the concentration of sodium salt scale preventive agent preferably become 1mg/L or more, more preferably become 5mg/L with
Mode that is upper, further preferably becoming 50mg/L or more as 10mg/L or more, particularly preferably is added in water system.Sodium in water
The concentration of salt scale preventive agent be required concentration more than, so as to improve sodium salt scale generation prevent effect.Wherein, sodium
The concentration of salt scale preventive agent can be lower than 1mg/L.
In one embodiment, 1000mg/L or less is become preferably with the concentration of sodium salt scale preventive agent, is more preferably become
500mg/L or less, add in water system further preferably as 300mg/L or less, particularly preferably as 200mg/L mode below
Add.The concentration of sodium salt scale preventive agent in water is required concentration or more, so as to improve preventing for sodium salt scale generation
Effect.Wherein, the concentration of sodium salt scale preventive agent can be more than 1000mg/L.
The water system of the application of sodium salt dirt prevention method is not particularly limited as long as the water system more than sodium ions content.
It, can be in water supply or carbonated drink in the processing in boiler kettle in the case where production equipment in one embodiment, such as paper pulp
It is directly added in drum.In the water-based processing of steel converter dust, it can be added to thickener processing pond, can also be added directly to
In recirculated water, or the slurry pool after dust arrester can also be added to.In addition, in the processing of the steaming solution kettle of pulping process, it can
To be added directly to kettle, it can also be added to kettle inner circulating tube line, or the white liquor fed in kettle can also be added to.In addition,
In processing in the Black Liquor Concentration process of pulping process, thin phenol water tank, thin phenol water liquor charging pipeline can be added to.
The water-based management method > of < 3.
The water-based management method of present embodiment is the method comprised the following steps: in same water system, adding sulfuric acid
The process and the above-mentioned process containing sulfosalicylic polymer of addition of sodium.
It should be noted that for add sodium sulphate process or add the process containing sulfosalicylic polymer period, these
The sequence of process (addition) is not particularly limited.
The water-based process for reducing viscosity > of < 4.
The water-based process for reducing viscosity of present embodiment is the method comprised the following steps: in same water system, adding sulfuric acid
The process of sodium and the process of the above-mentioned sodium salt scale preventive agent of addition.
It should be noted that for add sodium sulphate process or add the process containing sulfosalicylic polymer period, these
The sequence of process (addition) is not particularly limited.
The production equipment > of 5. paper pulp of <
Hereinafter, the water system of the application of the sodium salt scale preventive agent or sodium salt dirt prevention method as present embodiment, column
Example for the production equipment of paper pulp is illustrated, but the present invention is not by any restriction of following record.
Fig. 1 is the composition schematic diagram of the pulp manufacture system 1 using wooden sheet of one embodiment of the present invention.Pulp manufacture
System 1 has: steaming enzymatic hydrolysis system 10, black liquor system for handling 20, green liquor manufacturing system 30, green liquor system for handling 40, they are in Fig. 1
It is communicated with each other with the pipe that solid line indicates, constitutes the circulation path as a whole, the fluid in pulp manufacture system is recycled.In addition,
It steams enzymatic hydrolysis system 10, black liquor system for handling 20, green liquor manufacturing system 30, green liquor system for handling 40 and then has as not shown
Import the introduction part of equipment.Hereinafter, each component is described in detail.
[steaming enzymatic hydrolysis system]
The steaming solution kettle 11 that enzymatic hydrolysis system 10 has not shown heater with top and/or lower part is steamed, in the steaming solution kettle
11 downstream is equipped with paper pulp finish.In steaming solution kettle 11, puts into the wooden sheet of the raw material as paper pulp and contain sodium hydroxide
White liquor, carry out the steaming solution of wooden sheet.Resulting paper pulp (pulp) is transported to paper pulp finish, successively receives drift
White, copy paper process etc. manufactures paper.On the other hand, it in order to recycle sodium hydroxide etc., as the black liquor of waste liquid, is delivered to aftermentioned
Evaporator 21.
[black liquor system for handling]
Black liquor system for handling 20 successively has evaporator 21, boiler 22 from upstream.For black liquor, addition is used as viscosity reductant
Sodium sulphate, after being concentrated using evaporator 21, be delivered to boiler 22, burn in the boiler 22.In this way, containing in black liquor
Inorganic sodium melting, be discharged from the bottom of boiler 22 in the form of green liquor (melting matter).Green liquor after discharge is delivered to molten
Solve tank 31.
[green liquor manufacturing system]
Green liquor manufacturing system 30 successively has dissolving tank 31, green liquor clarification pond 32 and green liquor tank 33 from upstream.For green
Liquid is stirred by water and is dissolved in dissolving tank 31.It is added as a result, to sodium hydroxide, generates the green liquor for being rich in sodium carbonate.Dissolution
Not shown liquid-feeding pump is equipped in tank 31, green liquor is aspirated by the liquid-feeding pump, is delivered to green liquor clarification pond 32.It is residual for green liquor
The undissolved ingredient stayed is removed in green liquor clarification pond 32.Later, it is delivered to green liquor tank 33 and stores, be delivered to causticization later
System 41.
[green liquor system for handling]
Green liquor system for handling 40 successively has causticization system 41, white liquor clarification pond 42, white liquor tank 43 from upstream, in white liquor
The downstream of clarifying basin 42 has kiln 44.Causticization system 41, white liquor clarification pond 42, white liquor tank 43 communicate with each other, and constitute as a whole
The circulation path.Moreover, kiln 44 is connected to causticization system 41.
For green liquor, in causticization system 41, mixed with the calcium oxide supplied from kiln 44.Causticization system 41 includes coaster
411 and multiple causticizing reaction slots 412 for locateding downstream.It is delivered to green liquor (usually 90~100 DEG C, pH13 of coaster 411
~14) it is mixed with the calcium oxide of same supply to coaster 411.In this way, calcium oxide generates calcium hydroxide with water cure.It is defeated later
When sending to causticizing reaction slot 412, the sodium carbonate in green liquor reacts with calcium hydroxide, generates sodium hydroxide and calcium carbonate.
The obtained white liquor is transported to white liquor clarification pond 42.In the white liquor clarification pond 42, by insoluble calcium carbonate
After settling and separating, white liquor is stored in white liquor tank 43, is recycled to steaming solution kettle 11 later and recycles.On the other hand, after separation
Calcium carbonate is recycled in kiln 44, and is roasted, and is restored to calcium oxide, is reused in causticization system 41.
[introduction part]
Introduction part for example positioned at steaming enzymatic hydrolysis system 10 or black liquor system for handling 20 and imports sodium salt scale preventive agent.
It is such as above-mentioned in black liquor system for handling 20, the sodium sulphate as viscosity reductant is added, sodium ion exists with high concentration.So
Afterwards, water system is concentrated using evaporator 21, so that sodium ion is precipitated in the form of sodium sulphate, sodium carbonate, forms sodium salt scale.And
And the problem of thermal efficiency is worried due to the sodium salt scale.In view of this, it is being imported from the sodium salt scale preventive agent that introduction part imports
Position and inhibit scale downstream.In the present invention, " scale-deposit-preventing " is not particularly limited, such as refers to, the formation of pre- scale-deposit-preventing/attached
, or the scale being attached to is removed.
Imported parts can be any part of aforesaid fluid flow path, preferably require to inhibit the hair of problem caused by scale
Raw position or its upstream.Such as steaming solution kettle 11, boiler 22 can be directed into.
Embodiment
Hereinafter, showing embodiment, the present invention is more specifically illustrated, but the present invention is not by any of following embodiment
It limits.It should be noted that 2- acrylamide-2-methyl propane sulfonic sodium is abbreviated and makees " AMPS ", 3- alkene in embodiment below
Propoxyl group -2- hydroxyl -1- propanesulfonate brief note makees " HAPS ".
[experimental implementation]
(embodiment 1)
In the black liquor acquired from the Black Liquor Concentration kettle in kraft pulp manufacturing works, (concentration 20% contains 5 matter of sodium sulphate
Measure %) in, add acrylic acid/AMPS copolymer (molar ratio=50/50 acrylic acid/AMPS, no as sodium salt scale preventive agent
It is saturated sulfonic acid system monomer/whole monomer molar ratio (hereinafter referred to as " molar ratio ")=50, Mw=3000g/mol), make its at
For 100mg/L.It is put into 1L stainless steel beaker, is heated with IH heater, be concentrated while with 180rpm stirring, obtain concentrate.
Concentrate is burnt into Multipurpose teapot special-purpose metal net (61mm) filtering with nine paddy, measures quality of the quality relative to black liquor of residue
(hereinafter referred to as " residue rate ").
(embodiment 2)
As sodium salt scale preventive agent, using acrylic acid/AMPS copolymer, (molar ratio=70/30 acrylic acid/AMPS is rubbed
That ratio=70, Mw=5000g/mol), in addition to this, residue rate is measured similarly to Example 1.
(embodiment 3)
As sodium salt scale preventive agent, using acrylic acid/AMPS copolymer, (molar ratio=80/20 acrylic acid/AMPS is rubbed
That ratio=80, Mw=5000g/mol), in addition to this, residue rate is measured similarly to Example 1.
(embodiment 4)
As sodium salt scale preventive agent, using acrylic acid/AMPS copolymer, (molar ratio=90/10 acrylic acid/AMPS is rubbed
That ratio=90, Mw=5000g/mol), in addition to this, residue rate is measured similarly to Example 1.
(embodiment 5)
As sodium salt scale preventive agent, using acrylic acid/AMPS copolymer (molar ratio=95/5 acrylic acid/AMPS, mole
Than=95, Mw=5000g/mol), in addition to this, residue rate is measured similarly to Example 1.
(embodiment 6)
As sodium salt scale preventive agent, using acrylic acid/AMPS copolymer (molar ratio=98/2 acrylic acid/AMPS, mole
Than=98, Mw=5000g/mol), in addition to this, residue rate is measured similarly to Example 1.
(embodiment 7)
As sodium salt scale preventive agent, using acrylic acid/AMPS copolymer, (molar ratio=80/20 acrylic acid/AMPS is rubbed
That ratio=80, Mw=500g/mol), in addition to this, residue rate is measured similarly to Example 1.
(embodiment 8)
As sodium salt scale preventive agent, using acrylic acid/AMPS copolymer, (molar ratio=80/20 acrylic acid/AMPS is rubbed
That ratio=80, Mw=15000g/mol), in addition to this, residue rate is measured similarly to Example 1.
(embodiment 9)
As sodium salt scale preventive agent, using acrylic acid/AMPS copolymer, (molar ratio=80/20 acrylic acid/AMPS is rubbed
That ratio=80, Mw=100000g/mol), in addition to this, residue rate is measured similarly to Example 1.
(embodiment 10)
As sodium salt scale preventive agent, using acrylic acid/HAPS copolymer, (molar ratio=85/15 acrylic acid/HAPS is rubbed
That ratio=85, Mw=7000g/mol), in addition to this, residue rate is measured similarly to Example 1.
(embodiment 11)
As sodium salt scale preventive agent, kayexalate (molar ratio 100, M are usedw=3000g/mol), except this it
Outside, residue rate is measured similarly to Example 1.
(comparative example 1)
Without using sodium salt scale preventive agent, in addition to this, residue rate is measured similarly to Example 1.
(comparative example 2)
As sodium salt scale preventive agent, acrylate homopolymer (molar ratio=0, M are usedw=5000g/mol), in addition to this,
Residue rate is measured similarly to Example 1.
(comparative example 3)
As sodium salt scale preventive agent, maleic acid homopolymer (molar ratio=0, M are usedw=2000g/mol), in addition to this,
Residue rate is measured similarly to Example 1.
(comparative example 4)
As sodium salt scale preventive agent, maleic acid/acrylic copolymer (maleic acid/acrylic acid molar ratio=70/ is used
30, molar ratio=0, Mw=5000g/mol), in addition to this, residue rate is measured similarly to Example 1.
(comparative example 5)
As sodium salt scale preventive agent, maleic acid/acrylic copolymer (maleic acid/acrylic acid molar ratio=30/ is used
70, molar ratio=0, Mw=5000g/mol), in addition to this, residue rate is measured similarly to Example 1.
The chemical substance of sodium salt scale preventive agent used in Examples 1 to 8 and comparative example 1~8 is shown in table 1.
[table 1]
[experimental result]
The residue rate (%) measured in embodiment 1~11 and the Comparative Examples 1 to 5 is shown in table 2.So it is found that in water system
Addition contains sulfosalicylic polymer, and the sulfosalicylic polymer that contains is using unsaturated sulfonic acid system monomer as monomer, thus with un-added situation
It compares, the generation of scale can be inhibited.In addition we know, using weight average molecular weight be 700g/mol or more and 70000g/mol with
Under and the molar ratio of unsaturated sulfonic acid system monomer be that 3 moles of % or more contain sulfosalicylic polymer, thus with acrylic acid, Malaysia
Acid is monomer and the polymer phase ratio for not having sulfo group, can inhibit the generation of sodium salt scale.
[table 2]
| Residue rate (%) | |
| Embodiment 1 | 0.11 |
| Embodiment 2 | 0.07 |
| Embodiment 3 | 0.08 |
| Embodiment 4 | 0.10 |
| Embodiment 5 | 0.78 |
| Embodiment 6 | 1.8 |
| Embodiment 7 | 4.7 |
| Embodiment 8 | 0.99 |
| Embodiment 9 | 4.9 |
| Embodiment 10 | 0.08 |
| Embodiment 11 | 0.15 |
| Comparative example 1 | 5.2 |
| Comparative example 2 | 2.2 |
| Comparative example 3 | 1.1 |
| Comparative example 4 | 1.3 |
| Comparative example 5 | 1.7 |
Description of symbols
1 pulp manufacture system
10 steam enzymatic hydrolysis system
11 steam solution kettle
20 black liquor system for handling
21 evaporators
22 boilers
30 green liquor manufacturing systems
31 dissolving tanks
32 green liquor clarification ponds
33 green liquor tanks
40 green liquor system for handling
41 causticization systems
42 white liquor clarification ponds
43 white liquor tanks
44 kilns
411 coasters
412 causticizing reactions
Claims (13)
1. a kind of sodium salt scale preventive agent, it includes: at least contain sulfosalicylic polymer using unsaturated sulfonic acid system monomer as monomer.
2. sodium salt scale preventive agent according to claim 1, wherein the weight average molecular weight containing sulfosalicylic polymer is
700g/mol or more and 70000g/mol or less.
3. sodium salt scale preventive agent according to claim 1 or 2, wherein will constitute described all single containing sulfosalicylic polymer
In the case that the summation of the molal quantity of body is set as 100 moles of %, the unsaturated sulfonic acid system containing sulfosalicylic polymer is constituted
The molal quantity of monomer is 3 moles of % or more.
4. sodium salt scale preventive agent according to any one of claim 1 to 3, wherein unsaturated sulfonic acid system monomer is
Selected from vinyl sulfonic acid, allyl sulphonic acid, 2- acrylamide-2-methyl propane sulfonic, 3- allyloxy -2- hydroxyl -1- sulfonic acid, 2-
Methacrylamide -2- methyl propane sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, acrylamide methviium sulfonic acid and their alkali
One or more of metal salt or ammonium salt.
5. sodium salt scale preventive agent according to any one of claim 1 to 4, wherein the sulfosalicylic polymer that contains is at least
Using unsaturated sulfonic acid system monomer and unsaturated carboxylic acid system monomer as the copolymer of monomer.
6. sodium salt scale preventive agent according to claim 5, wherein unsaturated carboxylic acid system monomer is selected from by propylene
In the group that acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and their alkali metal salt, ammonium salt form
1 kind or more.
7. a kind of sodium salt dirt prevention method, sodium salt dirt described in any one of claims 1 to 6 is added in water system to be prevented
Agent.
8. sodium salt dirt prevention method according to claim 7, wherein become 1mg/ with the concentration of the sodium salt scale preventive agent
L or more and 1000mg/L mode below is added to water system.
9. sodium salt dirt prevention method according to claim 7 or 8, wherein the water system includes the sulfuric acid of 1 mass % or more
Sodium.
10. sodium salt dirt prevention method according to any one of claims 7 to 9, wherein the water system is kraft pulp system
Make the black liquor in process.
11. a kind of water-based viscosity reductant, it includes: sodium sulphate；With, at least using unsaturated sulfonic acid system monomer be monomer contain sulfo group
Polymer.
12. a kind of water-based management method comprising following process:
In same water system,
Add sodium sulphate process and
Addition is at least using unsaturated sulfonic acid system monomer as the process containing sulfosalicylic polymer of monomer.
13. a kind of water-based process for reducing viscosity comprising following process:
In same water system,
Add sodium sulphate process and
Addition is at least using unsaturated sulfonic acid system monomer as the process containing sulfosalicylic polymer of monomer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016229198A JP6365639B2 (en) | 2016-11-25 | 2016-11-25 | Sodium salt scale inhibitor, sodium salt scale prevention method, aqueous viscosity reducing agent, aqueous management method, and aqueous viscosity reducing method |
| JP2016-229198 | 2016-11-25 | ||
| PCT/JP2017/029467 WO2018096737A1 (en) | 2016-11-25 | 2017-08-16 | Sodium salt scale-preventing agent, sodium salt scale-preventing method, aqueous system viscosity-reducing agent, aqueous system management method, and aqueous system viscosity-reducing method |
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| CN110023253A true CN110023253A (en) | 2019-07-16 |
| CN110023253B CN110023253B (en) | 2022-09-09 |
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| CN201780070999.9A Active CN110023253B (en) | 2016-11-25 | 2017-08-16 | Agent for preventing sodium salt scale, method for preventing sodium salt scale, viscosity-reducing agent for water system, method for managing water system, and method for reducing viscosity of water system |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6365639B2 (en) |
| CN (1) | CN110023253B (en) |
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| JP2022047852A (en) * | 2020-09-14 | 2022-03-25 | 栗田工業株式会社 | Scale prevention agent and scale prevention method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2208936A1 (en) * | 1996-07-09 | 1998-01-09 | Hakuto Co., Ltd. | Scale deposit inhibitor for kraft digesters and method for controlling scale deposition in kraft digisters |
| CN1665853A (en) * | 2002-06-26 | 2005-09-07 | 施托克豪森有限责任公司 | Copolymers for avoiding deposits in water supply systems, production and use thereof |
| US20070062879A1 (en) * | 2003-07-23 | 2007-03-22 | Talbot Robert E | Scale inhibition in water systems |
| CN101538815A (en) * | 2008-03-17 | 2009-09-23 | 栗田工业株式会社 | Scale inhibitor in green liquor manufacturing system, inhibiting method and green liquor manufacturing system |
| CN101675191A (en) * | 2007-05-10 | 2010-03-17 | 纳尔科公司 | The method of the dirt deposition in monitoring and inhibition of pulp factory evaporimeter and the inspissator |
| WO2014157139A1 (en) * | 2013-03-29 | 2014-10-02 | 栗田工業株式会社 | Scale inhibiting method and magnesium hydroxide scale inhibitor for reverse osmosis membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ242970A (en) * | 1991-05-31 | 1994-12-22 | Calgon Corp | Composition for deposit control in a paper-making black liquor system comprising a mixture of acid group-containing polymer(s) and amine- or ammonium-containing polymer(s) |
-
2016
- 2016-11-25 JP JP2016229198A patent/JP6365639B2/en active Active
-
2017
- 2017-08-16 WO PCT/JP2017/029467 patent/WO2018096737A1/en active Application Filing
- 2017-08-16 CN CN201780070999.9A patent/CN110023253B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2208936A1 (en) * | 1996-07-09 | 1998-01-09 | Hakuto Co., Ltd. | Scale deposit inhibitor for kraft digesters and method for controlling scale deposition in kraft digisters |
| CN1665853A (en) * | 2002-06-26 | 2005-09-07 | 施托克豪森有限责任公司 | Copolymers for avoiding deposits in water supply systems, production and use thereof |
| US20070062879A1 (en) * | 2003-07-23 | 2007-03-22 | Talbot Robert E | Scale inhibition in water systems |
| CN101675191A (en) * | 2007-05-10 | 2010-03-17 | 纳尔科公司 | The method of the dirt deposition in monitoring and inhibition of pulp factory evaporimeter and the inspissator |
| CN101538815A (en) * | 2008-03-17 | 2009-09-23 | 栗田工业株式会社 | Scale inhibitor in green liquor manufacturing system, inhibiting method and green liquor manufacturing system |
| WO2014157139A1 (en) * | 2013-03-29 | 2014-10-02 | 栗田工業株式会社 | Scale inhibiting method and magnesium hydroxide scale inhibitor for reverse osmosis membrane |
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| Publication number | Publication date |
|---|---|
| CN110023253B (en) | 2022-09-09 |
| WO2018096737A1 (en) | 2018-05-31 |
| JP2018083176A (en) | 2018-05-31 |
| JP6365639B2 (en) | 2018-08-01 |
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