CN1056440A - A kind of improved Physical Absorption decarburization or doctor treatment - Google Patents
A kind of improved Physical Absorption decarburization or doctor treatment Download PDFInfo
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- CN1056440A CN1056440A CN 91107434 CN91107434A CN1056440A CN 1056440 A CN1056440 A CN 1056440A CN 91107434 CN91107434 CN 91107434 CN 91107434 A CN91107434 A CN 91107434A CN 1056440 A CN1056440 A CN 1056440A
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Abstract
The invention discloses a kind of improved Physical Absorption decarburization or doctor treatment, after in physical absorbent " third carbon ", adding the additive of 0.5-6% (weight ratio), not only can make " third carbon " system have good corrosion mitigating effect, and can accelerate its absorption rate greatly and increase its absorptive capacity, do not influence its desorption properties simultaneously again.Said additive is tertiary alcohol amine, tertiary amines, nitrogen heterocyclic ring compounds and their mixture.
Description
The present invention relates to a kind of physical absorption process that from admixture of gas, removes carbon dioxide (decarburization) or hydrogen sulfide (desulfurization).
The industrial organic solvent that successfully adopts is as carbon dioxide (decarburization) in the physical absorbent absorption and separation mist or hydrogen sulfide (desulfurization).Propene carbonate is compared as absorbent with water as physical absorbent, and it is bigger to have an absorption coefficient, and power consumption is lower, and the characteristics of technical comparative maturity again are so obtained bigger development.But there is a critical defect in this method, be when water content is higher in the system, the heavy corrosion that can cause equipment material, as water content in propene carbonate greater than the 4%(weight ratio) time, in the presence of sour gas, the corrosion rate of carbon steel material is increased by 10 times when anhydrous, when being in weak solution (when the propene carbonate weight concentration only is 10%), its corrosion rate can increase to more than 180 times.Accumulating over a long period of heavy corrosion not only caused equipment corrosion perforation, and corrosion product is trapped in the system, causes the deterioration of system operating state.
The objective of the invention is to: keeping under the prerequisite of propene carbonate as the whole advantages of physical absorbent, overcoming the shortcoming of the heavy corrosion that it causes owing to mixing of moisture content in process of production inevitably.For this reason, inventor's imagination adds a class additive in propylene carbonate ester, it had both had good corrosion inhibition, can increase propene carbonate (industrial be called for short habitually " third carbon " again significantly, for composing a piece of writing conveniently, intend adopting " third carbon " to represent propene carbonate below) to CO
2Or H
2The absorption rate of S and absorptive capacity, but do not influence its desorption rate, thus can give full play to " third carbon " value as the commercial Application of physical absorbent.
Design of the present invention is such: on the basis of basic maintenance original " third carbon " absorption technique, add interpolation Liu that more than one have corrosion inhibition and improve absorptive capacity and absorption rate double effects, absorb CO thereby optimize " third carbon "
2Or H
2The production technology of S.
" third carbon " system that the present invention is directed to can quicken the drawback to carbon steel equipment material heavy corrosion under the condition of aqueous acidic atmosphere, require added additive to have following characteristic:
(1) have alkalescent, (" third carbon " absorbs moisture CO to suppress acid medium
2, H
2Form acid medium behind the S) to the erosion of material,, make system pH value be in middle condition (or near middle condition) as far as possible, thereby play good corrosion mitigating effect owing to the introducing of additive.
(2) have good stable, promptly requiring to add intrasystem additive is stable to " third carbon " absorbent, does not impel " third carbon " hydrolysis.
(3) have and absorb cooperative effect preferably, under the synergy of additive and " third carbon ", can accelerate absorption rate and increase absorptive capacity, and not influence the desorption properties of dissolved gas.
Above each point is only taken into account the premises for the optimum principle of additive therefor of the present invention, could completely reach purpose of the present invention in the garden.
The present invention also is achieved in that under the guidance of above-mentioned design, by a large amount of experimental verifications, proof adds more than one additives, as tertiary alcohol amine, tertiary amines, nitrogen heterocyclic ring compounds and their mixture, the requirement that all can satisfy inhibition and improve absorptive capacity and absorption rate.
Said tertiary alkanolamine compounds can be N methyldiethanol amine [CH
3-N(C
2H
4OH)
2], triethanolamine [(C
2H
4OH)
3N], dimethylethanolamine [(CH
3)
2NC
2H
4OH], dimethyl propanol amine [(CH
3N
3CH
6OH] or their mixture.
Said tertiary amine compounds can be tri-n-butyl amine [(C
4H
9)
3N], triethylenediamine [(CH
2)
6N
2], tripropyl amine (TPA) [(C
3H
7)
3N] and their mixture.
Said nitrogen heterocyclic ring compounds can be 2-picoline (C
6H
7N), 3-picoline (C
6H
7N), 4-picoline (C
6H
7N), 2,4 lutidines (C
7H
9N), 1,4 lupetazin (C
6H
14N
2) and their mixture.
Mentioned reagent is commercially available chemically pure reagent.As consider the source and the economy of raw material, the most suitable with triethanolamine so.
The consumption of additive is the 0.5-6%(weight ratio), when at room temperature operating, be advisable with 1.0-4%.
To adopt the method for contrast further to illustrate content of the present invention below:
1, the corrosion mitigating effect behind the adding additive in the system, available relative corrosion inhibition rate η represents that it is defined as follows:
η= (K
o e)/(K
e)
Wherein: K
0 eCorrosion rate during for not doping (mm/y).
K
eBe the corrosion rate (mm/y) behind the adding additive.
The assay method of material corrosion speed can be measured (concrete grammar is omitted) by known conventional weight-loss method.
(1) table 1 reaches the 4%(weight ratio for water content in the system, under) the operating mode, absorbs CO with " third carbon " down together
2The time, the corrosion mitigating effect behind the adding additive.
Table 1
" third carbon " % water % additive % K
0 eOr K
eη
a
196.0 4.0 0 1.3×10
-21.0
b
195.5 4.0 0.5 4.3-5.3×10
-33.0-2.5
c
195.0 4.0 1.0 2.4-2.9×10
-35.4-4.5
d
194.0 4.0 2.0 1.6-2.0×10
-38.1-6.5
In the table 1: a
1Contrast corrosion rate K during for not doping
0 e
b
1Corrosion rate K when adding 0.5% additive
eSaid additive is respectively: N methyldiethanol amine, triethanolamine, dimethylethanolamine, dimethyl propanol amine, tri-n-butyl amine, triethylenediamine, tripropyl amine (TPA), the 2-picoline, the 3-picoline, the 4-picoline, 2, the 4-lutidines, 1,4 lupetazins and above-mentioned any mixture that compound is formed more than two kinds are (as the mixture by triethanolamine+N-methyl diethanol is formed, 2-picoline+3-picoline+4-lutidines composition mixture, triethanolamine+2-picoline, dimethyl propanol amine+1,4-lupetazin or the like).
c
1Corrosion rate K when adding 1% additive
e, said additive homophase b
1
d
1Corrosion rate K when adding 2% additive
e, the same b of said additive
1
(2) table 2 reaches for water content in the system under 6% the operating mode and absorbs CO
2The time, the corrosion mitigating effect behind the adding additive.
Table 2
" third carbon " % water % additive % K
0 eOr K
eη
a
294 6 0 3.1×10
-21.0
b
293.25 6 0.75 7.6-8.5×10
-34.1-3.6
c
292.5 6 1.5 7.3-8.2×10
-34.2-3.8
d
291 6 3.0 1.5-1.8×10
-320.7-17.2
In the table 2: a
2Contrast corrosion rate K during for not doping
0 e
b
2Corrosion rate K when adding 0.75% additive
e, the explanation that said additive is done with table 1.
c
2Corrosion rate K when adding 1.5% additive
e, the explanation that said additive is done with table 1.
d
2Corrosion rate K when adding 3% additive
e, the explanation that said additive is done with table 1.
(because the explanation that the experiment additive therefor is all done with table 1, so following narration is omitted).
Because different its corrosion rates of additive is different, so at table 1(b
1, c
1, d
1) and table 2(b
2, c
2, d
2) in provided respectively under their scope of corrosion rate with.
(3) table 3 reaches for water content in the system under 8% the operating mode and absorbs CO
2The time, the corrosion mitigating effect behind the adding additive.
Table 3
" third carbon " % water % additive % K
0 eOr K
eη
a
392 8 0 7.7×10
-21
b
391 8 1 4.2-4.7×10
-318.3-16.4
c
390 8 2 3.0-3.4×10
-325.7-22.6
d
388 8 4 2.7-2.9×10
-328.5-26.6
In the table 3: a
3Contrast corrosion rate K during for not doping
0 e
b
3For adding the corrosion rate K behind 1% additive
e
c
3For adding the corrosion rate K behind 2% additive
e
d
3For adding the corrosion K behind 4% additive
e
(4) table 4 reaches the 90%(weight ratio for water content in the system) operating mode under absorb CO
2The time, the corrosion mitigating effect behind the adding additive.
Table 4
" third carbon " % water % additive % K
0 eOr K
eη
a
410 90 0 2.1×10
-11
b
410 89 1 2.3-3.1×10
-29.1-6.8
In the table 4: a
4Contrast corrosion rate K during for not doping
0 e
b
4For the corrosion rate K of 1% additive
e
By table 1-table 4 as seen, add a small amount of additive and can suppress CO effectively
2Acid system is to the corrosion of carbon steel material, and its corrosion mitigating effect is significant, particularly dilute phase (refer to water content reach～90% o'clock because CO during not doping
2Acid system is very serious to the corrosion of material, has then played corrosion inhibition effectively after adding 1% additive) in the system, the inhibition effect of additive is more outstanding.The consumption that increases additive can further reduce corrosion rate, but has not had this necessity from the anti-corrosion angle of material, has reached the requirement (corrosion rate≤0.05mm/y) of inhibition because of minor amounts of additives.
(5) table 5 reaches the 8%(weight ratio for system's water content) operating mode under absorb H
2During S, the corrosion mitigating effect behind the adding additive.
Table 5
" third carbon " % water % additive % K
0 eOr K
eη
a
592 8 0 89.5×10
-21
b
591 8 1 7.8-8.8×10
-311.5-10.2
c
590 8 2 7.2-8.1×10
-3124-110
d
588 8 4 6.8-7.0×10
-3131-128
Wherein: a
5Contrast corrosion rate K during for not doping
0 e
b
5For adding the corrosion rate K behind 1% additive
e
c
5For adding the corrosion rate K behind 2% additive
e
d
5For adding the corrosion rate K behind 4% additive
e
By table 5 as seen, behind the additive of adding 2%, can make H
2The acid system of S to the corrosion rate of carbon steel material by 89.5 * 10
-2Mm/y(is not anti-corrosion) drop to 7.2-8.1 * 10
-3Mm/y(is anti-corrosion), its relative corrosion inhibition rate reaches 124-110, has reached the requirement of inhibition, and the consumption that increases additive can further reduce corrosion rate.
(6) table 6 reaches for water content in the system under the operating mode of (weight ratio) about 90% and absorbs H
2During S, add the corrosion mitigating effect of a small amount of additive.
Table 6
" third carbon " % water % additive % K
0 eOr K
eη
a
610 90 0 21.4×10
-21
b
610 89 1 10.8-12.4×10
-21.98-1.72
c
610 88 2 2.1-2.8×10
-210.1-7.6
Wherein: a
6Contrast corrosion rate K during for not doping
0 e
b
6For adding the corrosion rate K behind 1% additive
e
c
6For adding the corrosion rate K behind 2% additive
e
By table 6 as seen: add a small amount of additive, the dilute phase system is absorbed H
2S also has suitable corrosion mitigating effect.By corrosion rate relatively, add 2% additive after, material transfers anti-corrosion (less than 0.05mm/y) to by not anti-corrosion (greater than 0.1mm/y).
2, add the said additive of the present invention in the system after, the hydrolysis of " third carbon " absorbent is not had bad facilitation.
Usually a small amount of hydrolysis at a certain temperature, can take place with water in " third carbon " absorbent, as under 45 ℃ of constant temperature, and 92% " third carbon " absorbent and 8% water, the running continuously through 15 days proves that a small amount of " third carbon " is hydrolyzed by following equation:
C
3H
6CO
3+2H
2O ()/() C
3H
6（OH）
2+H
2CO
3，
Its hydrolysate propane diols [C
3H
6(OH)
2] content reaches the 2.8%(weight ratio) about.The content of hydrolysate propane diols can be used the assay determination of 102G gas chromatograph, and its absorption carrier is a white diatomite, and fixer is SE-30, and column temperature is 150 ℃.
Different moisture content " third carbon " and additive are mixed, be hydrolyzed according to above-mentioned similarity condition (under 45 ℃ of temperature, turning round continuously 15 days), measure the content of the propane diols in the hydrolysate then, the result is as shown in table 7.
Table 7
" third carbon " H
2Thing after the hydrolysis of O additive propane diols
The pH value of % % % % system
a
7-192 8 0 2.8 6.0
b
7-191 8 1 2.7-2.9 6.0-6.5
c
7-190 8 2 2.8-3.0 6.5-7.0
d
7-188 8 4 3.1-3.5 7.0-7.5
a
7-294 6 0 2.6 6.2
b
7-293.25 6 0.75 2.5-2.7 6.8-7.0
c
7-292.5 6 1.50 2.6-2.7 6.5-7.0
d
7-291.0 6 3 1.4-1.8 7.0-7.3
a
7-396 4 0 2.6 6.2
b
7-395.5 4 0.5 2.5-2.7 6.5-7.0
c
7-395 4 1 2.2-2.6 6.6-7.0
d
7-394 4 2 2.0-2.3 7.0-7.5
By table 7 as seen, in " third carbon ", add the said additive of the present invention, there is no adverse influence, conform to the requirement that additive should have good stability fully.
3, additive has the good absorption that helps to " third carbon " absorption system, and it not only can accelerate absorption rate, increases absorptive capacity, and does not influence the desorption properties of " third carbon ".Usually use in " third carbon ", under the constant temperature level pressure, in reactor, seal absorption CO
2The time, its CO
2Absorption rate can measure by known soap film flowmeter, every interval certain hour is measured once instantaneous absorption rate, promptly measures the milliliter number that the soap-film in the certain hour descends.CO
2Desorb can adopt known nitrogen to blow out method, in regenerator, carry out.Make the inertia source of the gas with nitrogen, enter in the regenerator nitrogen flushing continuously after the voltage stabilizing with the CO in the desorb lyosoption " third carbon " (abbreviation regenerated liquid) through decompression
2, every interval certain hour is measured the CO in the primary recycling liquid
2Concentration, CO in regenerated liquid
2Concentration reaches till the definite value.CO in the regenerated liquid
2Content analysis can adopt sour interpretation of the law: with quantified sample with 6NH
2SO
4Acidifying in analyzing bottle makes CO
2Desorb discharges, then with eudiometer tube read CO
2Volume, obtain CO in the regenerated liquid in view of the above
2Concentration.
(1) behind " third carbon " middle adding additive, its absorption rate and absorptive capacity can be shown in Table 8.
By table 8 as seen, containing 5%H
2Add the additive of different amounts in " third carbon " of O, all can improve CO
2Instantaneous absorption rate, simultaneously can increase " third carbon " absorbent to CO
2Absorptive capacity, that is:
A) as comparing with " third carbon " absorbent that contains 1% additive and " third carbon " absorbent that does not contain additive: its average absorption speed can improve 9-22%, and its absorptive capacity can increase 10-27%.
Table 8
" third carbon " H
2O additive absorption rate soak time absorptive capacity
% % % ml/l·s s ml/l
95 5 0 2.6
95 5 0 1.8 300 660
95 5 0 1.20 600 1110
95 5 0 0.40 1200 1590
95 5 0 0.15 1800 1755
95 5 0 0.05 2400 1815
95 5 0 0.05 3000 1845
94 5 1 2.8-3.0
94 5 1 1.9-2.1 300 705-765
94 5 1 1.25-1.45 600 1178-1297
94 5 1 0.5-0.65 1200 1703-1927
94 5 1 0.18-0.21 1800 1907-2185
94 5 1 0.09-0.11 2400 1988-2281
94 5 1 0.09-0.11 3000 2042-2347
92 5 3 3.3-3.6
Continuous table 8
" third carbon " H
2O additive absorption rate soak time absorptive capacity
% % % ml/l·s s ml/l
92 5 3 2.4-2.6 300 855-930
92 5 3 1.6-1.8 600 1455-1590
92 5 3 0.7-0.85 1200 2145-2385
92 5 3 0.3-0.40 1800 2445-2760
92 5 3 0.2-0.25 2400 2595-2955
92 5 3 0.11-0.14 3000 2688-3072
89 5 6 3.8-4.2
89 5 6 2.6-3.0 300 960-1080
89 5 6 1.8-2.0 600 1620-1830
89 5 6 0.8-1.0 1200 2400-2730
89 5 6 0.4-0.6 1800 2760-3210
89 5 6 0.2-0.3 2400 2940-3480
89 5 6 0.11-0.15 3000 3033-3615
Additive in the table 8 is all with the explanation of being done in the table 1-table 3.
B) as comparing with " third carbon " absorbent that contains 3% additive and " third carbon " absorbent that does not contain additive:
Its average absorption speed can improve 38-54%, and its absorptive capacity can increase 45-66%.
C) as comparing with " third carbon " absorbent that contains 6% additive and " third carbon " absorbent that does not contain additive: its average absorption speed improves 55-78%, and its absorptive capacity can increase 64-96%.
By as seen last: as single from improving " third carbon " system to CO
2The absorption effect, should select " third carbon " system that contains more additive for use, contain 6% additive " third carbon " system as selecting for use.Obviously as long as additive has enough solubility in " third carbon " system, can select the content of additive in the solubility so, also be feasible, so the amount of 6% additive here is not the protection domain of restriction claim.Concerning " third carbon " absorption system, above-mentioned various additives are under 40 ℃, distinguish as can be known from them and dissolving each other of " third carbon "-aqueous systems, solubility of additive can reach the 10%(weight ratio) more than, but should take into full account the economy of engineering, should do suitably to select.
(2) add 3% additive and not doping in " third carbon ", absorb CO respectively
2After reaching capacity, the desorption rate when carrying out desorb again can see Table 9.
By table 9 as seen: contain " third carbon " absorbent of 3% additive, the desorption rate of its desorption rate more not additivated " third carbon " absorbent is fast, after 16 minutes (960s), and CO wherein
2Residual quantity with not additivated " third carbon " absorbent in CO
2Residual quantity maintains an equal level.
In a word, by table 8, table 9 as seen, additive has good absorption cooperative effect with " third carbon " absorbent.Because the adding of additive both can have been quickened absorption rate greatly and increase absorptive capacity, and do not influence the CO in " third carbon "
2Desorption properties.
Table 9
The third carbon H
2CO in the O additive absorbent
2Desorption time
% % % residual quantity ml/l s
95 5 0 1845
95 5 0 1400 120
95 5 0 900 240
95 5 0 600 360
95 5 0 400 480
95 5 0 300 600
95 5 0 200 720
95 5 0 110 840
95 5 0 60 960
92 5 3 2979
92 5 3 1500-1700 120
92 5 3 950-1050 240
92 5 3 650-750 360
92 5 3 450-500 480
92 5 3 320-360 600
92 5 3 210-230 720
92 5 3 110-120 840
92 5 3 60-70 960
Additive in the table 9 is all with the explanation of being done in the table 1-table 3
In sum, additive preferred for this invention by many-sided experiment contrast, proves their the equal requirements that can satisfy optimization " third carbon " absorption technique, and its effect is very remarkable.
Claims (3)
1, a kind of improved Physical Absorption decarburization or doctor treatment, from admixture of gas, remove carbon dioxide or hydrogen sulfide by propene carbonate as the physics vapor, it is characterized in that: add more than one tertiary alcohol amine, tertiary amines, nitrogen heterocyclic ring compounds and their mixture additive in the physical absorbent propene carbonate, additivated weight ratio is 0.5-6%.
2, the method for claim 1, it is characterized in that said additive is N methyldiethanol amine, triethanolamine, dimethylethanolamine, dimethyl propanol amine, tri-n-butyl amine, triethylenediamine, tripropyl amine (TPA), 2-picoline, 3-picoline, 4-picoline, 2,4 lutidines, 1,4 lupetazin and by above-mentioned wantonly mixture that compound is formed more than two kinds.
3, method as claimed in claim 1 or 2 is characterized in that content of additive is the 1-4%(weight ratio in the propene carbonate).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107434 CN1031979C (en) | 1991-06-29 | 1991-06-29 | Modified decarbonizing or desulfurizing process by physical absorption |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107434 CN1031979C (en) | 1991-06-29 | 1991-06-29 | Modified decarbonizing or desulfurizing process by physical absorption |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1056440A true CN1056440A (en) | 1991-11-27 |
| CN1031979C CN1031979C (en) | 1996-06-12 |
Family
ID=4908772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91107434 Expired - Fee Related CN1031979C (en) | 1991-06-29 | 1991-06-29 | Modified decarbonizing or desulfurizing process by physical absorption |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1031979C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104928C (en) * | 1996-06-20 | 2003-04-09 | 中国石化辽阳石油化纤公司 | Acidic gas absorbent and preparation method thereof |
| CN102451612A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工集团公司 | Method for removing hydrogen sulfide in gas by non-aqueous solvent |
| CN104436997A (en) * | 2013-09-17 | 2015-03-25 | 中国石油化工股份有限公司 | Method for inhibiting degradation of desulfurization amine absorbent |
| CN106381182A (en) * | 2016-09-27 | 2017-02-08 | 中国石油化工股份有限公司 | Liquid absorbent for removing hydrogen sulfide and application thereof |
| CN112023625A (en) * | 2019-06-04 | 2020-12-04 | 中石化南京化工研究院有限公司 | Solvent and method for efficiently inhibiting equipment corrosion in carbon dioxide capture process |
| CN114367169A (en) * | 2020-10-15 | 2022-04-19 | 北京荣华康都环境技术有限公司 | Flue gas renewable desulfurization device and method |
| CN114367173A (en) * | 2020-10-15 | 2022-04-19 | 北京荣华康都环境技术有限公司 | Liquid sponge desulfurizer |
-
1991
- 1991-06-29 CN CN 91107434 patent/CN1031979C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104928C (en) * | 1996-06-20 | 2003-04-09 | 中国石化辽阳石油化纤公司 | Acidic gas absorbent and preparation method thereof |
| CN102451612A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工集团公司 | Method for removing hydrogen sulfide in gas by non-aqueous solvent |
| CN104436997A (en) * | 2013-09-17 | 2015-03-25 | 中国石油化工股份有限公司 | Method for inhibiting degradation of desulfurization amine absorbent |
| CN106381182A (en) * | 2016-09-27 | 2017-02-08 | 中国石油化工股份有限公司 | Liquid absorbent for removing hydrogen sulfide and application thereof |
| CN106381182B (en) * | 2016-09-27 | 2019-04-19 | 中国石油化工股份有限公司 | A kind of liquid-absorbant and its application for removing hydrogen sulfide |
| CN112023625A (en) * | 2019-06-04 | 2020-12-04 | 中石化南京化工研究院有限公司 | Solvent and method for efficiently inhibiting equipment corrosion in carbon dioxide capture process |
| CN114367169A (en) * | 2020-10-15 | 2022-04-19 | 北京荣华康都环境技术有限公司 | Flue gas renewable desulfurization device and method |
| CN114367173A (en) * | 2020-10-15 | 2022-04-19 | 北京荣华康都环境技术有限公司 | Liquid sponge desulfurizer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1031979C (en) | 1996-06-12 |
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