CN100528763C - Oxygen scavenger and boiler water treatment chemical - Google Patents
Oxygen scavenger and boiler water treatment chemical Download PDFInfo
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- CN100528763C CN100528763C CNB2007100044921A CN200710004492A CN100528763C CN 100528763 C CN100528763 C CN 100528763C CN B2007100044921 A CNB2007100044921 A CN B2007100044921A CN 200710004492 A CN200710004492 A CN 200710004492A CN 100528763 C CN100528763 C CN 100528763C
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Abstract
The present invention provides a plurality of oxygen purificant and a boiler water treating agent comprising the purificant. Each oxygen purificant respectively comprises the following active components, a heterocyclic compound comprising N-substituted amino group on the ring or the water-soluble salt thereof; a heterocyclic component represented by the formula (A); a heterocyclic component represented by the formula (B); an azodiamide; a heterocyclic compound with N-substituted amino group or the salt thereof and hydroxybenzene derivative. These compositions can further comprises neutral amine, alkaline reagent and/or water-soluble polymer to form the boiler water treating chemical preparation.
Description
The application divides an application, and the applying date of original application is on November 28th, 1997, and application number is 97114370.6, and its denomination of invention is " oxygen scavenger and a boiler water treatment chemical ".
Technical field
The present invention relates to oxygen scavenger, relate to more precisely and can remove the oxygen scavenger that is dissolved in water oxygen effectively, this oxygen scavenger is used in particular for suppressing corrosion by removing the oxygen that is dissolved in the drinking-water in boiler systems.In addition, the boiler water treatment chemical that the present invention relates to comprise this oxygen scavenger and deviate from the bird nest chemical preparations.
Background technology
Dissolved oxygen in drinking-water becomes the boiler systems member (as boiler body, one of be arranged in the heat exchanger and the economizer at boiler body upwelling place and be arranged in boiler body following current place steam and condensate pipe) reason for corrosion, in order to suppress the corrosion of boiler systems, handle the dissolved oxygen of removing in drinking-water by the deoxygenated of boiler drinking-water.
Dissolved oxygen is removed in conventional use chemical treatment and physical treatment, is widely used with oxygen scavenger such as hydrazine (N as for chemical treatment
2H
2), S-WAT (Na
2SO
3), azanol group or carbohydrate add the method in the feedwater, what intend usefulness in JPB S59-42073 and JPA H6-23394 is the reagent that contains azanol group and neutral amine.
Yet hydrazine is shady for the mankind's safety, so the problem that is treated as of hydrazine.
Because the reaction between S-WAT and the oxygen is too fast, so before S-WAT adds in the drinking-water, being dissolved in the S-WAT that water neutralization is stored in the container just reacts with airborne oxygen, thereby reduce the concentration of its effective constituent, therefore, the problem of existence is that S-WAT does not produce the effect of effectively removing dissolved oxygen sometimes.Because contain reaction product sulfate ion in the drinking-water with the S-WAT processing, so another problem is to cause corrosion and scale easily as S-WAT and oxygen.
The problem that also has be when the azanol group is added in the drinking-water and with boiler in the oxygen reaction time, azanol produces acid as nitric acid, thus minimizing is to the effect of corrosion inhibition of boiler body.
The defective that carbohydrate has is to be difficult to measure its residue concentration in feedwater, thereby is difficult to control correct add-on and carbohydrate produces foul smell to steam.
The someone proposes to use azo-compound as oxygen scavenger, has for example proposed 2, the two (N of 2-azo, N '-dimethylene isobutyl amidine), 2, two (isobutyl-acid amides)-2 hydrates, 4 of 2-azo, 4-azo two (4-cyano group caproic acid) and 2, two (2-amidino groups-propane)-HCl of 2-azo.
These azo-compounds are removed dissolved oxygen separately expeditiously, yet the defective of azo-compound is to produce various organic substances such as formic acid and acetate in drum boiler and steam, thereby quality of steam and purity are caused disadvantageous effect.
Summary of the invention
First purpose of the present invention provides a kind of oxygen scavenger of novelty, and described oxygen scavenger can be removed the dissolved oxygen of supplying with in the human high degree of safety boiler drinking-water effectively.
Second purpose of the present invention provides a clock and has oxygen scavenger as the N-substituted-amino group heterogeneous ring compound of effective constituent, described effective constituent not only can demonstrate the effect that removes oxygen fully to drinking-water line, boiler body or steam and the condensate line of high-temperature water, and the drinking-water line of water at low temperature is also demonstrated the effect that removes oxygen fully.
The 3rd purpose of the present invention provides a kind of chemicals of handling the novelty of feedwater, and this chemicals demonstrates to boiler body with for steam and condensation pipe corrosive restraining effect.
The 4th purpose of the present invention provides a kind of boiler water treatment chemical, this chemicals has the high effect of corrosion inhibition by the heterogeneous ring compound with N-substituted-amino group, and under the liquid state that contains this composition reagent, demonstrate the excellent effect of corrosion inhibition and scale restraining effect.
The effective constituent that the oxygen scavenger first aspect is characterised in that it is made up of the heterogeneous ring compound that has the N-N key on its ring in fact.
The oxygen scavenger second aspect is characterised in that its effective constituent is made up of the heterogeneous ring compound with N-substituted-amino group or its salt.
The oxygen scavenger third aspect is characterised in that its effective constituent is made up of the following formula heterogeneous ring compound:
(wherein, a, b be satisfy relational expression " 2≤a+b≤5 " 0 and 5 between integer).
The oxygen scavenger fourth aspect is characterised in that the heterogeneous ring compound composition that its effective constituent is expressed from the next in fact:
(wherein, R
1, R
2, R
3, R
4Can be same to each other or different to each other, represent any one in the following groups separately: hydrogen, have the low alkyl group of 1-8 carbon atom and also have the aryl of 1-8 carbon atom, and X represents in the following groups any one: hydrogen, amino, alkyl and dialkyl amino group with 1-8 carbon atom and have in the low alkyl group or aryl of 1-8 carbon atom).
Oxygen scavenger the 5th aspect is characterised in that its effective constituent is made up of azodicarbonamide in fact.
The oxygen scavenger of above-mentioned 1-5 aspect can be by the preparation of assigning in conjunction with two or more one-tenth.
For the amount of above-mentioned each side effective constituent without limits, and can change the amount of above-mentioned each side effective constituent with the concentration that is suitable for dissolved target oxygen in water, yet, with respect to 1 liter drinking-water, common amount is between 0.001 to 1000mg, between preferred 1 to 300mg.
Oxygen scavenger the 6th aspect is characterised in that and comprises heterogeneous ring compound or its salt and the hydroxy derivative with N-substituted-amino group.
In the oxygen scavenger aspect the 6th, because the katalysis of hydroxy derivative, make heterogeneous ring compound with N-substituted-amino group or its salt even in the drinking-water line of water at low temperature, also can demonstrate excellent deoxidation effect.
It is the chemicals of the processing feedwater of feature that the 7th aspect provides with heterogeneous ring compound with N-substituted-amino group and neutral amine.
It is the chemicals of the processing feedwater of feature that eight aspect provides with the heterogeneous ring compound with N-substituted-amino group and neutral amine or its salt and alkaline reagents and/or water soluble (CO) polymers.
Description of drawings
Fig. 1 is expression embodiment 36,37 and reference example 6-8 result's figure; With
Fig. 2 is expression embodiment 45-49 and reference example 21 results' figure.
Embodiment
1, first aspect
The effective constituent that the oxygen scavenger first aspect is characterised in that it is made up of the heterogeneous ring compound that has the N-N key on its ring, and preferably this included heterogeneous ring compound is following formula one at least:
: 1,3-dimethyl-5-pyrazolone
: urazole
Above-mentioned heterogeneous ring compound can separately or be used in combination.
Embodiment 1-10
The effect of first aspect oxygen scavenger has been tested as follows:
Oxygen-saturated softening water in the air under the room temperature is fed in the vapour generator test autoclave, and under following condition, operates this autoclave so that steam to take place:
Temperature: 185 ℃, pressure: 1Mpa, quantity of steam: 12 liters/hour, blow rate: 10%.
Fully the steam of condensation generation obtains water of condensation, and then, by the concentration that the dissolved oxygen sensing instrumentation is decided the dissolved oxygen in the water of condensation, the value that obtains is used as the data of reference example 1.
On the other hand, remove oxygen scavenger is added to the drinking-water China and foreign countries, under same condition, produce steam, then, also measure the dissolved oxygen concentration in the steam condensate, the difference of value that obtains and reference example 1 data be can be regarded as is (extraction) amount of drawing gas, and be can be regarded as with the ratio of drawing gas of reference example data to be the rate of drawing gas (%).
As for each embodiment of 1-10 is that the heterogeneous ring compound that table 1 shows is dissolved in the above-mentioned softening water, the aqueous solution with preparation preliminary assay concentration, then, this aqueous solution is fed in the drinking-water, the concentration of heterogeneous ring compound in the drinking-water is controlled to concentration as shown in table 1 by the fixed piston-type pump.
The results are shown in the table 1.
[table 1]
2, second aspect
The oxygen scavenger of second aspect is characterised in that its effective constituent is made up of the heterogeneous ring compound with N-substituted-amino group or its water-soluble salt, and preferred this included heterogeneous ring compound is following formula one at least:
: the amino high piperidines of N-;
As its salt, and for example above-mentioned heterogeneous ring compound and aliphatic carboxylic acid (as succsinic acid, pentanedioic acid, hexanodioic acid, gluconic acid, oxyacetic acid, lactic acid, oxysuccinic acid, tartrate or citric acid) or the water-soluble salt of poly carboxylic acid (as preferred use polyacrylic acid), but unrestricted to its salt.
Above-mentioned heterogeneous ring compound or its salt can separately or be used in combination.
Embodiment 11-21
Remove to use outside the effective constituent (in drinking-water, this oxygen scavenger has the concentration of heterogeneous ring compound shown in the table 2) of heterogeneous ring compound shown in the table 2, use with the same method of the foregoing description 1-10 and carry out deoxidation treatment among each embodiment as oxygen scavenger.The results are shown in the table 2.
[table 2]
3, the third aspect
The oxygen scavenger of the third aspect is characterised in that its effective constituent is made up of the following formula heterogeneous ring compound:
Preferred this included heterogeneous ring compound is following formula one at least:
Above-mentioned heterogeneous ring compound or its salt can separately or be used in combination.
Embodiment 22-27
Remove to use outside the effective constituent (in drinking-water, this oxygen scavenger has the concentration of heterogeneous ring compound shown in the table 3) of heterogeneous ring compound shown in the table 3, use with the same method of the foregoing description 1-10 and carry out deoxidation treatment among each embodiment as oxygen scavenger.The results are shown in the table 3.
[table 3]
4, fourth aspect
The oxygen scavenger of fourth aspect is characterised in that the heterogeneous ring compound composition that its effective constituent is expressed from the next in fact:
In this effective constituent of fourth aspect oxygen scavenger, for example, preferably use R
1, R
2, R
3, R
4Representative have 1-8 carbon atom low alkyl group methyl and also have phenyl or tolyl in the aryl of 1-8 carbon atom, in addition, preferably use X to represent and have the alkyl of 1-8 carbon atom and the methyl or the amino methyl of dialkyl amino group.
Preferred this included heterogeneous ring compound is following formula one at least:
(R
1, R
2, R
3, R
4With X be hydrogen entirely)
: 5,6-diaminostilbene, 3-dimethyl uracil
(R
1, R
2Be hydrogen, R
3, R
4Be methyl, X is amino)
Above-mentioned heterogeneous ring compound or its salt can separately or be used in combination.
Embodiment 28-34
Remove to use outside the effective constituent (in drinking-water, this oxygen scavenger has the concentration of heterogeneous ring compound shown in the table 4) of heterogeneous ring compound shown in the table 4, use with the same method of the foregoing description 1-10 and carry out deoxidation treatment among each embodiment as oxygen scavenger.The results are shown in the table 4.
[table 4]
5, the 5th aspect
The oxygen scavenger of the 5th aspect is characterised in that its effective constituent is azodicarbonamide (NH
2CON=NCONH
2).
The advantage of azodicarbonamide is: because azodicarbonamide do not produce any organic substance as formic acid and acetate, therefore do not change the quality of water in the boiler and keep the purity of generation steam.
Embodiment 35, reference example 2-5
Remove shown in the table 5 and add outside the effective constituent (in drinking-water, this effective constituent has the concentration of 150ml/L) of azo-compound as oxygen scavenger, use with the same method of the foregoing description 1-10 and carry out deoxidation treatment in this embodiment and each reference example.The results are shown in the table 5.
Primary product in the analysis generation steam and the primary product in the autoclave the results are shown in the table 5 respectively.
[table 5]
| Azo-compound | The concentration (mg/L) of flocculation oxygen in water | The amount of removing (mg/L) | The ratio of removing (%) | Principal product in the steam | Principal product in the autoclave | |
| Embodiment 35 | Azodicarboamide | 0.35 | 7.90 | 95.8 | Carbonic acid gas, ammonia | - |
| Reference example 1 | And do not add | 8.25 | - | - | - | - |
| Reference example 2 | 2,2-azo two (N, N '-dimethylene isobutyl amidine) | 1.05 | 7.20 | 87.3 | Acetone, methylamine, Virahol | Formic acid, acetate, Virahol |
| Reference example 3 | 2, two (isobutyl-acid amides) dihydrates of 2-azo | 0.25 | 8.00 | 97.0 | Acetone, carbonic acid gas, Virahol, ammonia | Formic acid, acetate, Virahol |
| Reference example 4 | 4,4-azo two (4-cyano group caproic acid) | 0.35 | 7.90 | 95.8 | Carbonic acid gas | Various organic acids |
| Reference example 5 | 2, two (2-amidine propane) HCl of 2-azo | 0.45 | 7.85 | 95.2 | Acetone, Virahol, ammonia | Formic acid, Virahol |
As in table 5, obviously seeing, all azo-compounds are removed dissolved oxygen expeditiously, particularly azodicarbonamide does not produce the organic acid that changes drinking water quality in the autoclave (being equivalent to boiler drum), to such an extent as to preferably use the oxygen scavenger of azodicarbonamide as boiler drinking-water.
6, the 6th aspect
The oxygen scavenger of the 6th aspect is characterised in that and comprises heterogeneous ring compound or its salt and the hydroxy derivative with N-substituted-amino group.
In the oxygen scavenger aspect the 6th, because the katalysis of hydroxy derivative, make heterogeneous ring compound with N-substituted-amino group or its salt even in the drinking-water line of water at low temperature, also can demonstrate excellent deoxidation effect.
The heterogeneous ring compound that preferably has N-substituted-amino group is one of following compounds at least: 1-amino-pyrrolidine, 1-amino-4-methylpiperazine, 1-amino piperidine, the amino high piperidines of 1-, 1,4-diamino piperazine, amino morpholine of N-and morpholino Shuan Veins; As its salt, and for example above-mentioned heterogeneous ring compound and aliphatic carboxylic acid (as succsinic acid, gluconic acid, pentanedioic acid, hexanodioic acid, oxyacetic acid, lactic acid, oxysuccinic acid, tartrate or citric acid) or the water-soluble salt of poly carboxylic acid (as preferred use polyacrylic acid), but unrestricted to it.These heterogeneous ring compounds and salt can be suitable for separately or be used in combination.
As hydroxy derivative, can use quinhydrones, 2,3-dimethyl-1,4-quinhydrones, catechol, the 4-tert-butyl catechol, pyrogallol, 1,2,4-hydroxybenzene, gallic acid, the 2-amino-phenol, 2, the 4-diaminophenol, the 4-amino-phenol, still, hydroxy derivative is not limited thereto.Hydroxy derivative also can be suitable for separately or knot uses.
Though, they can be injected respectively by making heterogeneous ring compound or its salt mix the oxygen scavenger that can prepare the 6th aspect with hydroxy derivative with N-substituted-amino group.
The amount of the 6th aspect oxygen scavenger can be to change with the concentration that adapts as dissolved oxygen in the boiler systems drinking-water of object and the condition face of other water, yet, drinking-water with respect to 1 liter, usually the heterogeneous ring compound with N-substituted-amino group or its salt and the hydroxy derivative that add (between preferred 0.01 to 300mg, more preferably 0.02 to 100mg) between 0.001 to 1000mg.
The heterogeneous ring compound with N-substituted-amino group aspect the 6th in the oxygen scavenger or effective ratio of its salt and hydroxy derivative are heterogeneous ring compound or its salt with N-substituted-amino group: hydroxy derivative=1: 0.001-10 (weight ratio).When hydroxy derivative is less than this ratio, be not enough to provide the enhancement of hydroxy derivative of the present invention, promptly, be not enough to provide the deoxygenated effect that strengthens water at low temperature, on the other hand, when hydroxy derivative during more than this ratio, the cost of processing improves pro rata for the enhancing of effect.
With by in the heterogeneous ring compound with alkaline N-substituted-amino group and the mode of the hydroxy derivative of little acid, the oxygen scavenger of the 6th aspect is dissolved in the water, when being difficult to the dissolved oxygen scavenging agent, add as the alkali of caustic soda (NaOH) with the solubleness of raising oxygen scavenger.
Though the characteristics of the oxygen scavenger of the 6th aspect are to comprise heterogeneous ring compound or its salt and the hydroxy derivative with N-substituted-amino group, but, if desired, also can add other oxygen scavenger or corrosion inhibitor, as hydrazine, S-WAT, succsinic acid or Portugal's glyconic acid or dispersion agent in addition, chelate compound, rust cleaning chemicals, or the mixture of above-mentioned some of them.
The oxygen scavenger of the 6th aspect can be used for various types of boiler systemss effectively, as low pressure, medium and high pressure boiler systems, and all unrestricted to boiler pressure, boiler type or all kinds of drinking-water.
Embodiment 36,37, reference example 6-8
The softening water of 1 liter of Atsugi water tap tap water is charged in the Erlenmeyer flask, and after with NaOH pH being controlled at 9.0, in 60 ℃ water bath with thermostatic control, it is stirred two hours so that it is by airborne oxygen saturation.(by Obisfair Co., " MOCA3600 " that Ltd makes) measures dissolved oxygen concentration at this moment by dissolved oxygen meter, and the result is 4.75mg/L.
After being added to the chemicals of the amount of Table 6 in the Erlenmeyer flask of water respectively, stir them fully, in the three furan bottles with the solution impouring 200ml capacity that obtains, cover the furan bottle cap, there is not the space in it, then it is transferred in 60 ℃ the water bath with thermostatic control so that solution reaction, in the preliminary assay time (5,10,20 minutes) when passing through the furan bottle is taken out from water bath with thermostatic control, measure the concentration of dissolved oxygen in the solution by dissolved oxygen meter, after adding chemicals, calculate the residue ratio of dissolved oxygen each sample solution with the proportional meter that adds the dissolved oxygen concentration before the chemicals.These operate in the nitrogen atmosphere and carry out rapidly.
The results are shown among table 6 and Fig. 1.
The result obviously shows by using as having the quinhydrones (HQ) of 1-amino-pyrrolidine (APY) or 1-amino-4-methylpiperazine (AMPI) hydroxy derivative or have N-substituted-amino heterogeneous ring compound, has strengthened deoxygenation greatly.
[table 6]
(note) Ex: embodiment
Co: reference example
The APY:1-amino-pyrrolidine
AMPI:1-amino-4-methylpiperazine
HQ: quinhydrones
7, the 7th aspect
The 7th aspect provides to comprise the chemicals of the processing feedwater that heterogeneous ring compound with N-substituted-amino group and neutral amine are feature.
The neccessary composition of this respect chemicals is heterogeneous ring compound and the neutral amine with N-substituted-amino group.
Heterogeneous ring compound with N-substituted-amino group by with boiler in the dissolved oxygen reaction and display go out excellent deoxygenated effect, to suppress the corrosion of boiler body.
Chemicals also has following useful function except that the above-mentioned function of the heterogeneous ring compound with N-substituted-amino group.
Heterogeneous ring compound with N-substituted-amino group has the ability of the reduced iron of evaporable characteristic and excellence, and in other words, heterogeneous ring compound has the function that suppresses the iron oxidation, promptly suppresses iron rot.
Owing to be included in the function of the above-mentioned heterogeneous ring compound in the steam condensate, so the steam condensate that produces with the chemical treatment feedwater of the 7th aspect can make steam condensate by the time lose the characteristic of corrosion pipeline, in addition, because be also included within the function of the neutral amine in the steam condensate, so, the PH of steam condensate is grasped at neutrality or alkaline range, thereby suppress the corrosive pipeline that phlegma passes through.
That is to say that the chemicals of this respect can either also can show the corrosive restraining effect at boiler body in steam and phlegma pipeline.
As the heterogeneous ring compound of N-substituted-amino group, can use any compound that can show as above-mentioned function and effect.For example, can preferably use the amino morpholine of N-, 1-amino-pyrroles alkyl, 1-amino-4-methylpiperazine, 1,4-diamino piperazine, 1-amino piperidine, the amino high piperidines of 1-, morpholino biguanides and above-mentioned heterogeneous ring compound and carboxylic acid are (as succsinic acid, gluconic acid, pentanedioic acid, hexanodioic acid, oxyacetic acid, lactic acid, oxysuccinic acid, tartrate or citric acid), the water-soluble salt of poly carboxylic acid (as preferred use polyacrylic acid), and these heterogeneous ring compounds and its salt can be suitable for separately or be used in combination.
As other neccessary composition of neutral amine, chemicals, can use the feedwater and the steam condensate that can make after the processing to be neutral or alkaline any compound.For example, cyclo-hexylamine, 2-amino-2-methyl-1-propanol, monoethanolamine, diethanolamine, morpholine, monoisopropanolamine, diethylethanolamine, dimethyl propanol amine, dimethylethanolamine and dimethyl propylamine, they can be suitable for separately or be used in combination.
By making heterogeneous ring compound and aforesaid neutral amine be mixed with the chemicals of the 7th aspect.
Can with the concentration that adapts as dissolved oxygen in the boiler systems of the object drinking-water and the conditional decision blending ratio of other water, yet, drinking-water with respect to 1 liter, usually heterogeneous ring compound and neutral amine respectively add by following amount: between 0.001 to 1000mg, between preferred 0.01 to 300mg, more preferably 0.02 to 100mg.
Though the neccessary composition of the 7th aspect chemicals is heterogeneous ring compound and the neutral amine with N-substituted-amino group, but, also can add other known oxygen scavenger or corrosion inhibitor, as hydrazine, S-WAT, succsinic acid or gluconic acid or known in addition dispersion agent, chelate compound, rust cleaning chemicals, or the mixture of above-mentioned some of them.
The chemicals of the 7th aspect can be used for various types of boiler systemss effectively, as low pressure, medium and high pressure boiler systems, and all unrestricted to boiler pressure, boiler type or all kinds of drinking-water.
Embodiment 38-44, reference example 9-20
At 40 ℃, the softening water of tap water in the oxygen-saturated water tap is charged in the test grill pan of 5 liters of capacity, and under following condition, boiler is operated, to produce steam:
Temperature: 183 ℃, pressure: 1Mpa, quantity of steam: 12 liters/hour and blow rate: 10%.
Make vapor condensation obtain phlegma, accurate phlegma is cooled to 50 ℃, then, feed in the post, deposit in post at first, above-mentioned test grill pan is steel (SS400 of a Japanese Industrial Standards) system sample, each length of side 50mm, wide 15mm and thick 1mm.Sample was soaked in described phlegma 96 hours.
Measure the sample etching extent respectively, to calculate the corrosion rate in feedwater and the phlegma.End value be representative by the feedwater of no chemical treatment index to sample generation extent of corrosion, the results are shown in Table 8 as reference example 9.
Should be noted that after the measurement operation concentration of nitrate ion and nitrite ion in the feedwater, the results are shown in the table 8.So that the mode that chemicals has definite concentration respectively in the table 7 in softening water is dissolved in it in above-mentioned softening water, with fixed displacement pump it is fed in the boiler then.
[table 7]
Under the condition identical with above-mentioned reference example 9, the steam condensate that the softening water of soluble chemistry composition takes place is done corrosion test, calculate the corrosion rate of sample.
In addition, the concentration of nitrate ion and nitrite ion in the feedwater the results are shown in the table 8 after the measurement operation.
[table 8]
Table 7 and table 8 clearly illustrate the following fact:
1), therefore is not suitable for suppressing the corrosion of boiler because comprise that the chemicals of azanol group (reference example 10-17) produces nitrate ion and nitrite ion in feedwater.
2) use heterogeneous ring compound to reduce the erosion rate of iron in the feedwater alone with N-substituted-amino group, in feedwater, do not produce nitrate ion and nitrite ion, yet, because the erosion rate of iron is still high in phlegma, to such an extent as to still produce the corrosion of steam and condensation pipe, so heterogeneous ring compound is improper.
3), in feedwater, all do not produce nitrate ion and nitrite ion with any in the embodiment chemicals, and in feedwater and phlegma, suppress the corrosion of iron effectively with the contrast of above-mentioned reference example.
8, eight aspect
The eight aspect boiler water treatment chemical is characterised in that and comprises heterogeneous ring compound or its salt and alkaline reagents and/or the water soluble (CO) polymers with N-substituted-amino group.
In the situation of water at low temperature, the heterogeneous ring compound of N-substituted-amino group or its salt have slower deoxygenated reaction under neutrallty condition; Under alkaline condition, has higher deoxygenated reaction.Therefore, even in the pipe line of water at low temperature, strengthen the deoxygenated effect of heterogeneous ring compound with alkaline reagents, its result is further to strengthen the deoxygenated effect of drinking-water line and reduce the amount that enters iron in the boiler.Enter iron that iron in the drinking-water and boiler vessel elutriation go out and attach to heating surface as the oxide compound body refuse of iron, the oxide compound body refuse of iron causes concentration cell or analogue to be beneficial to corrosion, and in the drinking-water line, the increase of the effect of corrosion inhibition can reduce anticaustic.
Even when hard component spills from tenderizer or ion exchange unit, reduce the corrosion that the oxide compound body refuse (by this body refuse diffusion function) by iron causes with water-soluble polymers and can further prevent the heating surface scaling.
Because by using neutral amine that the pH of steam condensate is controlled at neutrality or alkalescence, so, the corrosion of steam condensate pipeline (being the steam water shoot) suppressed.
As the heterogeneous ring compound that is used for eight aspect, preferably use the 1-amino-pyrrolidine, 1-amino-4-methylpiperazine, 1-amino piperidine, the amino high piperidines of 1-, 1,4-diamino piperazine, amino morpholine of N-and morpholino biguanides with N-substituted-amino group; As its salt, and for example above-mentioned heterogeneous ring compound and aliphatic carboxylic acid (as succsinic acid, pentanedioic acid, hexanodioic acid, gluconic acid, oxyacetic acid, lactic acid, oxysuccinic acid, tartrate or citric acid) or the water-soluble salt of poly carboxylic acid (as preferred use polyacrylic acid), but unrestricted to it.These heterogeneous ring compounds and its salt can be suitable for separately or be used in combination.
The alkaline reagents such as the sodium hydroxide that are used for eight aspect, potassium hydroxide, but unrestricted.These alkaline reagentss can be suitable for separately or be used in combination.
As the water-soluble polymers that is used for eight aspect, the preferred polyacrylic acid that uses, polymaleic acid, polyisobutene acid, the multipolymer of polyacrylic acid and acrylic acid amides, the multipolymer of vinylformic acid and hydroxyl allyloxy propane sulfonic acid, the multipolymer of vinylformic acid and 2-acrylamide-2-methyl propane sulfonic acid, with its salt, but unrestricted to it.These water-soluble polymerss can be suitable for separately or be used in combination.
As the neutral amine that is used for eight aspect, can use to make feedwater and steam condensate be neutral or alkaline any compound.For example, hexahydroaniline can preferably be used, 2-amino-2-methyl-1-propanol, monoethanolamine, diethanolamine, morpholine, monoisopropanolamine, dimethylethanolamine, diethylethanolamine, dimethyl propanol amine and dimethyl propylamine, they can be suitable for separately or be used in combination.
Though the eight aspect boiler water treatment chemical can prepare and further prepare by mixing neutral amine by above-mentioned N-substituted-amino heterogeneous ring compound or its salt are mixed with alkaline reagents and/or water-soluble polymers, but, if necessary, also it can be added respectively.
The amount of eight aspect boiler water treatment chemical can be to change with the condition of the concentration that adapts as dissolved oxygen in the boiler systems drinking-water of object and other water, yet, drinking-water with respect to 1 liter, usually the heterogeneous ring compound with N-substituted-amino group of (between preferred 0.01 to 300mg, more preferably 0.02 to 100mg) or its salt and alkaline reagents and/or water-soluble polymers between respectively adding 0.001 to 1000mg.
To such an extent as to especially preferably add alkaline reagents pH between 8 and 12 according to the boiler type.
When neutral alkali used with boiler water treatment chemical, with respect to 1 liter drinking-water, the amount of preferred neutral alkali was between 0.01 to 500mg, between 0.1 to 100mg.
In the eight aspect boiler water treatment chemical, preferably will have the heterogeneous ring compound of N-substituted-amino group or the ratio (by weight) of its salt and alkaline reagents and/or water-soluble polymers and be set as follows:
(1) when the heterogeneous ring compound with N-substituted-amino group or its salt and alkaline reagents use together, has heterogeneous ring compound or its salt of N-substituted-amino group: alkaline reagents=1: 0.01-20.
(2) when the heterogeneous ring compound with N-substituted-amino group or its salt and water-soluble polymers use together, has heterogeneous ring compound or its salt of N-substituted-amino group: water-soluble polymers=1: 0.01-20.
(3) when the heterogeneous ring compound with N-substituted-amino group or its salt and alkaline reagents and water-soluble polymers use together, has heterogeneous ring compound or its salt of N-substituted-amino group: alkaline reagents: water-soluble polymers=1: 0.01-20: 0.01-20.
Yet when using wherein neutral amine, preferred ratio is heterogeneous ring compound or its salt of N-substituted-amino group: neutral amine=1: 0.01-20 (by weight).
Though the neccessary composition of eight aspect boiler water treatment chemical is heterogeneous ring compound and alkaline reagents and/or water-soluble polymers and the neutral amine with N-substituted-amino group, but if necessary, also can add other known oxygen scavenger or corrosion inhibitor, as hydrazine, S-WAT, carbohydrate, succsinic acid, gluconic acid or the amine different with above-mentioned neutral amine, or known in addition dispersion agent, chelate compound, rust cleaning chemicals, or the mixture of above-mentioned some of them.
The boiler water treatment chemical of eight aspect can be used for various types of boiler systemss effectively, as low pressure, medium and high pressure boiler systems, and all unrestricted to boiler pressure, boiler type or all kinds of drinking-water.
Hereinafter, will eight aspect be described in more detail with some embodiment and reference example.
Embodiment 45-49, reference example 21
By adding five kinds of experimental liquids of preparation in 1 liter the deionized water as the sodium hydroxide of alkaline reagents, so that pH is respectively 8.0,9.0,10.0,11.0 and 12.0.It was stirred 1 hour in 60 ℃ water bath with thermostatic control, and in air, make it saturated, measure the concentration of dissolved oxygen with dissolved oxygen meter (by " MOCA3600 " of Obisfair manufacturing) respectively with oxygen.After adding the heterogeneous ring compound 1-amino-pyrrolidine (1-AP) of 100mg as N-substituted-amino group, stir them fully, in the furan bottle with the solution impouring 200ml capacity that obtains, cover the furan bottle cap, there is not the space in it, then, it is transferred in 60 ℃ the water bath with thermostatic control so that solution reaction, after 20 minutes, the furan bottle is taken out from water bath with thermostatic control, by the concentration of dissolved oxygen in the dissolved oxygen meter mensuration solution, calculate the residue ratio (embodiment 45-49) of dissolved oxygen each sample solution from the proportional meter that adds the later dissolved oxygen concentration before adding reagent of 1-amino-pyrrolidine.These operate in the nitrogen atmosphere and carry out rapidly.
With identical method (reference example), test with the experimental liquid of the pH6.8 that does not add sodium hydroxide, in contrast.
The results are shown among table 9 and Fig. 2 of this test.
The result obviously shows by using 1-amino-pyrrolidine and alkaline reagents as N-substituted-amino group heterogeneous ring compound to strengthen desoxydatoin greatly.
[table 9]
| Embodiment | The pH of test water | Add the 1-AP concentration (mg/L) of dissolved oxygen before | Add the 1-AP concentration (mg/L) of dissolved oxygen afterwards | Dissolved oxygen remove ratio (%) |
| Embodiment 45 | 8.0 | 4.30 | 3.55 | 17.4 |
| Embodiment 46 | 9.0 | 4.30 | 2.65 | 38.4 |
| Embodiment 47 | 10.0 | 4.30 | 1.60 | 62.8 |
| Embodiment 48 | 11.0 | 4.30 | 1.00 | 76.7 |
| Embodiment 49 | 12.0 | 4.30 | 0.70 | 83.7 |
| Reference example 21 | 6.8 | 4.30 | 4.05 | 5.8 |
Embodiment 50-55, reference example 22,23
At 40 ℃, 30mg is added in air in the softening water of oxygen-saturated water tap tap water as the 1-amino-pyrrolidine of N-substituted-amino group heterogeneous ring compound, the water that obtains is fed in the test grill pan of 5 liters of capacity, and under following condition, boiler is operated to produce steam, the time of operation is 240 hours
Condition:
Temperature: 183 ℃,
Pressure: 1Mpa,
Quantity of steam: 11 liters/hour
Blow rate: 10% and
Give the concentration of iron in the entry: 0.5m/L.
Sedimentary in drinking-water line, grill pan bag and steam water shoot at first is steel (SS400 of Japanese Industrial Standards) system sample, each length of side 50mm, wide 15mm and thick 1mm.Measure the sample extent of corrosion, to calculate corrosion rate.The results are shown in the table 10, the iron amount (amount of deposited iron) that contains in the ferriferous oxide that mensuration deposition sample is made in the boiler bag the results are shown in (reference example 22) in the table 10.
The chemical ingredients that shows in the table 10 is dissolved in the above-mentioned softening water,, then, it is fed in the boiler by using the fixed piston-type pump so that have the concentration that shows respectively shown in the table 10 in the softening water.
With above-mentioned same condition under, the steam condensate that the softening water of soluble chemistry composition takes place is carried out corrosion test, calculate the corrosion rate of sample and the amount of deposited iron, the results are shown in (embodiment 50-55, reference example 23) in the table 10.
Table 10 obviously show by use 1-amino-pyrrolidine and alkaline reagents and, or water-soluble polymers and further can the be enhanced effect of corrosion inhibition and scale removal effect of test neutral amine.
[table 10]
* 1-AP:1-amino-pyrrolidine
Water-soluble polymers: the multipolymer of vinylformic acid and hydroxyl propenyloxy group propane sulfonic acid
AMP:2-amino-2-methyl-1-propyl alcohol
As top description see, any oxygen scavenger can both be removed oxygen in water effectively in the 1-5 of the present invention aspect, when they are used as boiler drinking-water oxygen scavenger, wherein any can both inhibition by the boiler body of dissolved oxygen generation and the corrosion of steam and condensation pipe, therefore, each oxygen scavenger all has very high industrial applicibility.
In addition, the 5th aspect provides the oxygen scavenger that prevents to produce by product in boiler, is beneficial to not influence steam purity.
The 6th aspect provides the oxygen scavenger that strengthens deoxygenated effect in water at low temperature drinking-water line, and compares with conventional corrosion inhibitor, obviously is better than them in drinking water pipeline.
Though chemicals is a component reagent, but, the chemicals that feedwater is handled in the 7th aspect has shown the excellent effect of corrosion inhibition with respect to any boiler body and steam and condensate line, and this is because contain N-substituted-amino group heterogeneous ring compound and middle amine in the chemicals.
Though chemicals is a component reagent,, eight aspect provides the boiler water treatment chemical that not only has the excellent effect of corrosion inhibition but also have the scale removal effect.
Claims (4)
1, the heterogeneous ring compound represented of following formula is as the purposes of the oxygen scavenger of feedwater:
In the formula, R
1, R
2, R
3, R
4Be same to each other or different to each other, and represent following any one group separately: hydrogen, have the low alkyl group of 1-8 carbon atom and also have the aryl of 1-8 carbon atom, and following any one group of X representative: hydrogen, amino, alkyl or dialkyl amino group and have the low alkyl group or the aryl of 1-8 carbon atom with 1-8 carbon atom.
2, purposes according to claim 1, wherein, by R
1, R
2, R
3, R
4The low alkyl group with 1-8 carbon atom of representative is a methyl, by R
1, R
2, R
3, R
4The aryl with 1-8 carbon atom of representative is phenyl or tolyl, and alkyl with 1-8 carbon atom or the dialkyl amino group represented by X are methyl or amino methyl.
3, purposes according to claim 2, wherein, described compound is a 5-Urea,amino-pyrimidine.
4, purposes according to claim 2, wherein, described compound is 5,6-diaminostilbene, 3-FU dimethyl.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP318140/1996 | 1996-11-28 | ||
| JP31814096A JP3287243B2 (en) | 1996-11-28 | 1996-11-28 | Oxygen scavenger |
| JP63579/1997 | 1997-03-17 | ||
| JP138468/1997 | 1997-05-28 | ||
| JP288490/1997 | 1997-10-21 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97114370A Division CN1103748C (en) | 1996-11-28 | 1997-11-28 | Oxygen scavenger and boiler water treatment chemical |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN100999343A CN100999343A (en) | 2007-07-18 |
| CN100528763C true CN100528763C (en) | 2009-08-19 |
Family
ID=18095953
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100044917A Expired - Fee Related CN100528762C (en) | 1996-11-28 | 1997-11-28 | Oxygen scavenger and boiler water treatment chemical |
| CNB2007100044921A Expired - Fee Related CN100528763C (en) | 1996-11-28 | 1997-11-28 | Oxygen scavenger and boiler water treatment chemical |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100044917A Expired - Fee Related CN100528762C (en) | 1996-11-28 | 1997-11-28 | Oxygen scavenger and boiler water treatment chemical |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3287243B2 (en) |
| CN (2) | CN100528762C (en) |
| BR (1) | BR9706050A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6540923B2 (en) | 2000-12-05 | 2003-04-01 | Kurita Water Industries Ltd. | Oxygen scavenger |
| JP4950391B2 (en) * | 2001-06-27 | 2012-06-13 | 上野製薬株式会社 | Oxygen absorber |
| JP3855961B2 (en) | 2003-04-28 | 2006-12-13 | 栗田工業株式会社 | Oxygen absorber and deoxygenation method |
| JP4745990B2 (en) * | 2007-01-31 | 2011-08-10 | 三菱重工業株式会社 | Turbine equipment and initial switching method for oxygen treatment of turbine equipment |
-
1996
- 1996-11-28 JP JP31814096A patent/JP3287243B2/en not_active Expired - Lifetime
-
1997
- 1997-11-28 BR BR9706050A patent/BR9706050A/en not_active IP Right Cessation
- 1997-11-28 CN CNB2007100044917A patent/CN100528762C/en not_active Expired - Fee Related
- 1997-11-28 CN CNB2007100044921A patent/CN100528763C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| BR9706050A (en) | 1999-06-29 |
| CN100528762C (en) | 2009-08-19 |
| CN100999342A (en) | 2007-07-18 |
| JP3287243B2 (en) | 2002-06-04 |
| JPH10158872A (en) | 1998-06-16 |
| CN100999343A (en) | 2007-07-18 |
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