CN102505122A - Glauberite pipeline scale descaling agent and application thereof - Google Patents
Glauberite pipeline scale descaling agent and application thereof Download PDFInfo
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- CN102505122A CN102505122A CN2011102976471A CN201110297647A CN102505122A CN 102505122 A CN102505122 A CN 102505122A CN 2011102976471 A CN2011102976471 A CN 2011102976471A CN 201110297647 A CN201110297647 A CN 201110297647A CN 102505122 A CN102505122 A CN 102505122A
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- glauberite
- pipeline
- descaling agent
- dirt
- scale remover
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Abstract
The invention discloses a glauberite pipeline scale descaling agent and application thereof. The descaling agent comprises the following components in percentage by weight: 10-25% of NaOH, 5-15% of Na2S2O35H2O, and 0.05-0.5% of sodium polyacrylate. The descaling agent provided by the invention can be used for transforming insoluble CaSO4 into soluble Ca(OH)2 and Na2SO4; a proper amount of Na2S2O35H2O serving as a complexing agent is added and complexed with Ca<2+> in Ca(OH)2 to form a more stable complex, a new precipitate is prevented from generating, and a dissolution reaction is promoted to happen; a proper amount of EDTA (ethylene diamine tetraacetic acid) and a proper amount of polyacrylamide are added to realize a more remarkable scale inhibition effect; and acid is not contained in the components of the descaling agent, and no acid is generated in the descaling process, so that the descaling agent has small corrosive influence on a salt manufacturing pipeline and small influence on the mechanical performance of the salt manufacturing pipeline; and after being subjected to simple sediment treatment, a residual solution obtained after filtering can be returned to a bittern pre-treatment system, so that the alkaline solution in the residual solution can be utilized, so that sewage is hardly drained, and the descaling agent is environmentally-friendly.
Description
Technical field
The present invention relates to a kind of chemical detergent, particularly a kind of chemical detergent of removing glauberite.
Background technology
Glauberite is the double salt of sodium sulfate and calcium sulfate, and chemical formula is xNa
2SO
4YCaSO
4NH
2O.And the solubleness of calcium sulfate wherein in water is seen table 1.
The solubleness of table 1 calcium sulfate under differing temps
Visible by table 1, the solubleness of calcium sulfate in water is less, and has extreme value with variation of temperature.When temperature more than 40 ℃ the time, the solubleness of calcium sulfate in water is along with the rising of temperature reduces.Therefore, in heating tube,, when calcium ion in the solution and sulfate ion concentration are higher, precipitate easily and separate out because pipe surface temperature is high.
In the salt manufacturing industry, especially behind the vacuum salt production system operation some cycles, part salt making equipment (the particularly water back of Heat Room) can produce scale formation in various degree, and this is the ubiquitous problem of salt manufacturing industry.In order not influence normal production run, enhance productivity, need regularly carry out scale removal and handle.
The present inventor carries out the discovery of composition analyzing and testing to the pipeline dirt of vacuum salt production equipment especially; The composition of this dirt layer is mainly glauberite; And the classical group of this glauberite becomes calcium sulfate mass content >=60%, and sodium sulfate quality content >=10%, is main with calcium sulfate promptly.
To the research of glauberite dirt, people such as Zhu Jingquan utilize Na
2SO
4-CaSO
4-NaCl-H
2The O quarternary phase diagram has been set forth the physical and chemical condition that glauberite forms, and points out: because CaSO
4Solubleness very little, so the phase region of gypsum occupies most areas in whole phase region, the phase region of other material is then very little.In the glauberite phase region, Ca
2+And Na
+Mol ratio be 1:486～l:6920, the liquid phase that promptly forms glauberite is formed and will be had high Na+ content and extremely low Ca
2+Content, and the bittern in the salt industry satisfies such condition undoubtedly, has the condition that forms the glauberite dirt.
People such as Liu Chenglin point out, with the raising of temperature, and the range extension of glauberite phase region.Therefore, temperature is high more, helps separating out of glauberite more, and what glauberite dirt this can be interpreted as mainly precipitates in heating tube and separate out.Simultaneously, people such as Liu Chenglin point out that, glauberite and gypsum can precipitate simultaneously separates out, and both amount of substances are identical, whenever separate out 1 mol Na that is: under certain condition
2SO
4CaSO
4, separate out 1 mol Na simultaneously
2SO
4, in theory, this moment precipitation system in Na
2SO
4Content be 34.3%, CaSO
4Content be 65.7%, approaching with the composition of glauberite dirt in the heating tube.
Therefore, preliminary supposition, the formation of glauberite dirt is because the temperature of water back is higher in the heating tube, is generally 70～130 ℃, Ca in the bittern
2+And Na
+Mol ratio less, satisfy the condition that glauberite is separated out, and when sodium-chlor was separated out, saltcake and gypsum were separated out simultaneously.
And to the ducted typical glauberite dirt of salt manufacturing, present removing method mainly adopts the high pressure water descaling method, and the method that promptly adopts a kind of physics to wash away is removed, and is though this method is friendly to environment, high to the better simply equipment scale removal of structure efficient.But, to structure than the inapplicable high pressure water descaling method of complex apparatus, for the very high dirt layer of densification and hardness; Hydraulic pressure is too low to have satisfied not the scale removal requirement, and adopts higher hydraulic pressure, for the security existence influence of equipment; Equipment has ruined possibility, also just causes cost to increase indirectly.
If adopt the chemical cleaning method; Also there is not at present relevant research report; Trace it to its cause, be on the one hand owing to there is following technical barrier: calcium sulfate belongs to strong acid salt, therefore; Adopt traditional pickling descaling strong acid to being that main salt making equipment pipeline dirt solute effect is relatively poor with calcium sulfate; Because the material of water back material generally adopts titanium material or 2205DSS (i.e. 2205 duplex stainless steels), especially titanium that hydrogen embrittlement takes place in acidic medium easily, therefore traditional pickling descaling agent prescription can not be applicable to the present technique problem that solves simultaneously.
Summary of the invention
One of goal of the invention of the present invention is the problem to above-mentioned existence, provides a kind of being applicable to remove glauberite pipeline dirt and novel scale remover that can corrosion pipeline.
The technical scheme that the present invention adopts is such: a kind of glauberite pipeline dirt scale remover comprises following component by mass ratio:
NaOH： 10-25%
Na
2S
2O
3·5H
2O: 5-15%
ZX-I: 0.05-0.5%.
The contriver is through a large amount of experiments, and having selected a kind of is the scale remover of host with NaOH, and its scale removal mechanism is: CaSO
4+ 2NaOH=Ca (OH)
2+ Na
2SO
4
Promptly through reaction (its essence is solubilizing reaction), with insoluble CaSO
4Be converted into soluble Ca (OH)
2And Na
2SO
4In addition, in order to prevent new sedimentary generation, and from Ca (OH)
2The consideration of electrolytic equilibrium adds Na
2S
2O
35H
2O is as complexing agent, and confirmed a comparatively suitable add-on through a large amount of experiments, lets itself and Ca (OH)
2Ca
2+Carry out complexing, form more stable complex compound, prevent that new deposition from generating, and promote the generation of solubilizing reaction; But, through discovering, in this case, the Ca that part is tiny
2+Powder still can be reunited again and formed new dirt layer, so the present invention has also added the ZX-I (being PAAS) of 0.05-0.5%, because the contriver discovers an amount of ZX-I deposition is had dissemination, can prevent tiny Ca
2+Powder is reunited again and is formed the dirt layer.
As preferably: the EDTA that also comprises 0.01-0.2%.The adding of an amount of EDTA is complexing Ca (OH) further
2Ca
2+, prevent that new deposition from generating, and promote the generation of solubilizing reaction.
Further: the SEPIGEL 305 that also comprises 0.05-0.1%.The adding of an amount of SEPIGEL 305 can prevent better that new deposition from generating, and promotes the generation of solubilizing reaction.
Another object of the present invention provides a kind of application of above-mentioned glauberite pipeline dirt scale remover; The technical scheme that is adopted is: the usage quantity when being applied to the scale removal of glauberite pipeline dirt, employed scale remover is (10-50) with the mass ratio of dirt layer: 1.
As preferably: this scale remover is particularly useful for consisting of calcium sulfate mass content >=60%, and the glauberite pipeline of sodium sulfate quality content >=10% dirt.
In sum, owing to adopted technique scheme, the invention has the beneficial effects as follows: scale remover provided by the present invention can be with insoluble CaSO
4Be converted into soluble Ca (OH)
2And Na
2SO
4Add an amount of Na simultaneously
2S
2O
35H
2O is as complexing agent, lets itself and Ca (OH)
2In Ca
2+Carry out complexing, form more stable complex compound, prevent that new deposition from generating, and promote the generation of solubilizing reaction; The adding of an amount of EDTA and SEPIGEL 305 makes scale inhibition effect more obvious; Simultaneously, owing to do not contain acid in the moity of this Scale inhibitors, also do not generate acid in the scale removal process, so very little to the influence of salt manufacturing Corrosion of Pipeline, the influence to the salt manufacturing pipeline is also very little simultaneously.
In addition, the raffinate after the scale removal can be got back to the bittern pretreatment system and utilize alkali lye wherein after handling through simple sediment, does not almost have sewage discharge, environmental friendliness.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Embodiment 1:
(1) a kind of glauberite eliminating sludge in pipe agent, the prescription that is adopted consists of
NaOH：20g
Na
2S
2O
3.5H
2O：12g
H
2O：68g
Preparing method: with promptly getting in the water that directly is dissolved in above-mentioned quality after above-mentioned two kinds of accurate weighings of component.
During use, this scale remover is 30:1 with the ratio of dirt layer quality.
Embodiment 2:
The agent of a kind of glauberite eliminating sludge in pipe, the prescription that is adopted consists of
NaOH：10g
Na
2S
2O
3.5H
2O：5g
H
2O：85g
Preparing method: with promptly getting in the water that directly is dissolved in above-mentioned quality after above-mentioned two kinds of accurate weighings of component.
During use, this scale remover is 50:1 with the ratio of dirt layer quality.
Embodiment 3
The agent of a kind of glauberite eliminating sludge in pipe, the prescription that is adopted consists of
NaOH：25g
Na
2S
2O
3.5H
2O：15g
H
2O：60g
Preparing method: with promptly getting in the water that directly is dissolved in above-mentioned quality after above-mentioned two kinds of accurate weighings of component.
During use, this scale remover is 40:1 with the ratio of dirt layer quality.
Embodiment 4
The agent of a kind of glauberite eliminating sludge in pipe, the prescription that is adopted consists of
NaOH：25g
Na
2S
2O
3.5H
2O：15g
ZX-I: 0.05g
H
2O：59.95g
The preparation method: elder generation is configured to ZX-I 5% solution then with the accurate weighing of said components, under 80 ℃ water-bath, dissolves promptly to get again.
During use, this scale remover is 40:1 with the ratio of dirt layer quality.
Embodiment 5
The agent of a kind of glauberite eliminating sludge in pipe, the prescription that is adopted consists of
NaOH：25g
Na
2S
2O
3.5H
2O：15g
ZX-I: 0.5g
H
2O：59.5g
The preparation method: elder generation is configured to ZX-I 5% solution then with the accurate weighing of said components, under 80 ℃ water-bath, dissolves promptly to get again.
During use, this scale remover is 40:1 with the ratio of dirt layer quality.
Embodiment 6
The agent of a kind of glauberite eliminating sludge in pipe, the prescription that is adopted consists of
NaOH：25g
Na
2S
2O
3.5H
2O：15g
ZX-I: 0.25g
H
2O：59.75g
The preparation method: elder generation is configured to ZX-I 5% solution then with the accurate weighing of said components, under 80 ℃ water-bath, dissolves promptly to get again.
During use, this scale remover is 40:1 with the ratio of dirt layer quality.
Embodiment 7
The agent of a kind of glauberite eliminating sludge in pipe, the prescription that is adopted consists of
NaOH：25g
Na
2S
2O
3.5H
2O：15g
ZX-I: 0.05g
EDTA：0.01g
H
2O：59.94g
The preparation method: elder generation is configured to ZX-I 5% solution then with the accurate weighing of said components, under 80 ℃ water-bath, dissolves promptly to get again.
During use, this scale remover is 40:1 with the ratio of dirt layer quality.
Embodiment 8:
The agent of a kind of glauberite eliminating sludge in pipe, the prescription that is adopted consists of
NaOH：25g
Na
2S
2O
3.5H
2O：15g
ZX-I: 0.05g
EDTA：0.2g
H
2O：59.75g
The preparation method: elder generation is configured to ZX-I 5% solution then with the accurate weighing of said components, under 80 ℃ water-bath, dissolves promptly to get again.
During use, this scale remover is 40:1 with the ratio of dirt layer quality.
Embodiment 9
The agent of a kind of glauberite eliminating sludge in pipe, the prescription that is adopted consists of
NaOH：25g
Na
2S
2O
3.5H
2O：15g
ZX-I: 0.05g
EDTA：0.01g
SEPIGEL 305: 0.05g
H
2O：59.89g
The preparation method: elder generation is configured to ZX-I 5% solution then with the accurate weighing of said components, under 80 ℃ water-bath, dissolves promptly to get again.
During use, this scale remover is 40:1 with the ratio of dirt layer quality.
Embodiment 10
The agent of a kind of glauberite eliminating sludge in pipe, the prescription that is adopted consists of
NaOH：25g
Na
2S
2O
3.5H
2O：15g
ZX-I: 0.05g
EDTA：0.01g
SEPIGEL 305: 0.1g
H
2O：59.84g
The preparation method: elder generation is configured to ZX-I 5% solution then with the accurate weighing of said components, under 80 ℃ water-bath, dissolves promptly to get again.
During use, this scale remover is 40:1 with the ratio of dirt layer quality.
Embodiment 11
The agent of a kind of glauberite eliminating sludge in pipe, the prescription that is adopted consists of
NaOH：25g
Na
2S
2O
3.5H
2O：15g
ZX-I: 0.05g
EDTA：0.01g
SEPIGEL 305: 0.08g
H
2O：59.86g
The preparation method: elder generation is configured to ZX-I 5% solution then with the accurate weighing of said components, under 80 ℃ water-bath, dissolves promptly to get again.
Embodiment 12
Descale effect contrast is carried out the scale removal contrast experiment with the scale remover of embodiment 1-11 gained, and the dirt layer consists of during scale removal: the calcium sulfate mass content is 72%; Sodium sulfate quality content is 14%; All the other are crystal water and free-water, with 24 hours be point of observation, with descaling rate as the parameter of weighing descale effect; Said descaling rate is: (particle diameter is in the quality of 10mm with top after the quality-scale removal of dirt layer) * 100%/dirt layer quality, and the experimental result such as the table 2 that obtain:
Table 2: descale effect contrast and experiment
Embodiment 13
Descale effect contrast is carried out the scale removal contrast experiment with the scale remover of embodiment 1-11 gained, and the dirt layer consists of during scale removal: the calcium sulfate mass content is 85%; Sodium sulfate quality content is 10%; All the other are crystal water and free-water, with 24 hours be point of observation, with descaling rate as the parameter of weighing descale effect; Said descaling rate is: (particle diameter is in the quality of 10mm with top after the quality-scale removal of dirt layer) * 100%/dirt layer quality, and the experimental result such as the table 3 that obtain:
Table 3: descale effect contrast and experiment
Can find out from table 3:, adopt scale remover of the present invention still can reach good descale effect even the quality of calcium sulfate reaches 90% the glauberite pipeline dirt.
Embodiment 14
Scale remover of the present invention is tested for the salt manufacturing Corrosion of Pipeline
The scale remover prescription that present embodiment adopts embodiment 1,5,11 to be provided experimentizes, and adopts titanium material pipeline and 2205 duplex stainless steels (2205DSS) to experimentize respectively,
Table 4: scale remover of the present invention is to salt manufacturing Corrosion of Pipeline experimental result
Visible by table 4, titanium material and 2205DSS are all more stable in scale remover of the present invention, and promptly scale remover is very little to the influence of salt manufacturing Corrosion of Pipeline.
Embodiment 15
Scale remover of the present invention is for the hardness influence experiment of salt manufacturing pipeline
The scale remover prescription that present embodiment adopts embodiment 1,2,11 to be provided experimentizes, and adopts titanium material pipeline and 2205 duplex stainless steels (2205DSS) to experimentize respectively,
Table 5: experiment of hardness result
Visible by table 5, after the titanium material soaked in scale remover of the present invention, hardness had reducing to a certain degree; And with the increase of NaOH concentration, hardness further reduces, but the amplitude that reduces is less; Consider test error, think that the titanium material soaks in formula system after, performance does not have noticeable change.And after 2205DSS soaked in scale remover of the present invention, hardness changed hardly.
Claims (5)
1. glauberite pipeline dirt scale remover and application thereof is characterized in that: comprise following component by mass ratio:
NaOH： 10-25%
Na
2S
2O
3·5H
2O: 5-15%
ZX-I: 0.05-0.5%.
2. according to the said glauberite pipeline dirt of claim 1 scale remover, it is characterized in that: the EDTA that also comprises 0.01-1%.
3. according to the said glauberite pipeline dirt of claim 2 scale remover, it is characterized in that: the SEPIGEL 305 that also comprises 0.05-0.1%.
4. the application of any described glauberite pipeline dirt scale remover of claim 1 to 3, it is characterized in that: the usage quantity when being applied to the scale removal of glauberite pipeline dirt, employed scale remover is (10-50) with the mass ratio of dirt layer: 1.
5. the application of the described glauberite pipeline of claim 4 dirt scale remover is characterized in that: be applied to glauberite pipeline dirt glauberite consist of calcium sulfate mass content >=60% and sodium sulfate quality content >=10%.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110297647.1A CN102505122B (en) | 2011-10-08 | 2011-10-08 | Glauberite pipeline scale descaling agent and application thereof |
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| CN102505122A true CN102505122A (en) | 2012-06-20 |
| CN102505122B CN102505122B (en) | 2014-04-23 |
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| CN105238384A (en) * | 2015-10-30 | 2016-01-13 | 中国石油天然气股份有限公司 | Preparation method for precipitation inhibitor used for sandstone acidification |
| CN110143676A (en) * | 2019-06-13 | 2019-08-20 | 科得邦（江苏）环境科技有限公司 | The nontoxic scale preventative and preparation method thereof being concentrated for halogen transportation pipeline and bittern evaporation |
| CN111252913A (en) * | 2020-03-02 | 2020-06-09 | 西南交通大学 | Composite scale inhibitor for concrete drainage pipeline and application thereof |
| CN113751441A (en) * | 2021-09-09 | 2021-12-07 | 吉林吉恩镍业股份有限公司 | Method for cleaning scale on inner wall of evaporator in nickel sulfate production process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111252913A (en) * | 2020-03-02 | 2020-06-09 | 西南交通大学 | Composite scale inhibitor for concrete drainage pipeline and application thereof |
| CN113751441A (en) * | 2021-09-09 | 2021-12-07 | 吉林吉恩镍业股份有限公司 | Method for cleaning scale on inner wall of evaporator in nickel sulfate production process |
| CN113751441B (en) * | 2021-09-09 | 2022-10-11 | 吉林吉恩镍业股份有限公司 | Method for cleaning scale on inner wall of evaporator in nickel sulfate production process |
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