CN1052430C - Polyamine method for removing carbon dioxide and sulfide in gas - Google Patents
Polyamine method for removing carbon dioxide and sulfide in gas Download PDFInfo
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- CN1052430C CN1052430C CN93110579A CN93110579A CN1052430C CN 1052430 C CN1052430 C CN 1052430C CN 93110579 A CN93110579 A CN 93110579A CN 93110579 A CN93110579 A CN 93110579A CN 1052430 C CN1052430 C CN 1052430C
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- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 32
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229920000768 polyamine Polymers 0.000 title claims abstract description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 7
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims abstract description 37
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 8
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012190 activator Substances 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 47
- 238000005265 energy consumption Methods 0.000 abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000746 purification Methods 0.000 abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003345 natural gas Substances 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000008929 regeneration Effects 0.000 description 14
- 238000011069 regeneration method Methods 0.000 description 14
- 238000003795 desorption Methods 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000005261 decarburization Methods 0.000 description 6
- 229910000975 Carbon steel Inorganic materials 0.000 description 5
- 239000010962 carbon steel Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102000018779 Replication Protein C Human genes 0.000 description 2
- 108010027647 Replication Protein C Proteins 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000948268 Meda Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- AIOXPJUKHIPDKC-UHFFFAOYSA-N [C].[O].[S] Chemical compound [C].[O].[S] AIOXPJUKHIPDKC-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- -1 diazocyclohexane (piperazine) Chemical compound 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to a method for removing carbon dioxide and sulfide in mixed gas of synthetic ammonia, methanol, hydrogen production raw material gas, city gas, natural gas and the like by adding polyamine solution consisting of two secondary amines into N-methyldiethanolamine solution. It has the characteristics of high purification degree, low energy consumption of regenerative heat and the like.
The solution of the invention comprises three groups of components: the N-methyldiethanolamine accounts for 20 to 60 percent by weight. Suitable sulfur-free gases are: 1-5% by weight of piperazine and 1-10% by weight of diethanolamine; suitable sulfur-containing gases are two groups: 0.1-10% by weight of N-methyl-ethanolamine, 1-10% by weight of diethanolamine; 0.1-10% by weight of N-methyl-ethanolamine, 1-5% by weight of piperazine.
Description
The present invention belongs to the field of separation technology, and relates to the field of gas separating technology by chemical-physical absorption. The invention relates to a method for removing carbon dioxide and sulfide from acid mixed gas by using polyamine solution of composite N-Methyldiethanolamine (MDEA) containing double activators.
The N-methyldiethanolamine solution is widely applied to the removal of carbon dioxide and sulfide from mixed gas of synthesis ammonia, methanol, hydrogen production raw gas, city gas, natural gas and the like. General N-methyldiethanolamineCalled MDEA) solution with a gas mixture under pressure, CO2And the sulfide is absorbed by the solution, after which the solution is subjected to atmospheric desorption and steam stripping to cause CO to be formed2And the sulfide is desorbed from the MDEA solution. Absorption and desorption of CO with a simple MDEA solution2Low speed, high heat consumption, CO2The purification degree is low. Therefore, various catalysts or activators are added into the MDEA solution in foreign countries to overcome the defects.
Patent DE1,904,428(70 years) reports the addition of N-methyl-ethanolamine (MMEA) as activator. The addition of diazocyclohexane (piperazine) as activator is reported in patent DE2,551,717 (77). The solutions of these patents have fast absorption and desorption speed, low heat consumption and high purification degree. Has been applied to dozens of large-scale industrial devices abroad. However, the method is to add an activator to MDEA solution only and singly to improve the absorption of CO into the solution2The mass transfer rate coefficient of (1). While the latter patent absorbs more rapidly than the former patent, the latter patent doesDue to the low boiling point, the partial pressure of steam is high. Therefore, in process applications, a washing system is required to be added, otherwise the loss is high, and in addition, the concentration of the washing system in the solution cannot be too high, otherwise the carbon steel can be corroded.
In the invention, besides piperazine or MMEA is respectively added into MDEA solution, Diethanolamine (DEA) is also added to form a novel composite activator. The components play the following roles in the polyamine process solution:
1. N-Methyldiethanolamine (MDEA); it is a tertiary amine. Absorption of CO2The carbonate is generated after the reaction, so that the heating regeneration can be carried out, and the steam consumption is low and is only half of that of the primary amine and the secondary amine. Primary, secondary amine and CO2Generates rather stable carbamate, and MDEA has high thermal degradation resistance and chemical degradation resistance; the corrosion to carbon steel is basically avoided: the vapor pressure of the solution is low, so that no obvious vaporization loss exists when a high-concentration solution of 50 percent is used; nonpolar gases such as hydrogen, nitrogen, methanol and higher hydrocarbons have a relatively low solubility in solution. The loss of cleaned gas is low.
MDEA has a special isothermal solubility curve (see figure one). For comparison, a 25% Monoethanolamine (MEA) solution and physical solution were usedCO of Propylene Carbonate (PC) as agent2Solubility is also shown in figure one. As can be seen from the figure, CO2The partial pressure is reduced from 5 bar to 1 bar, so that the equilibrium load of the MDEA solution is 57NM3/M3The solution dropped to 27NM3/M3Release of 30NM from solution3CO2/M3And (3) solution. The corresponding numbers for MEA and PC solutions are 11 and 9.8NM, respectively3/M3And (3) solution. The effect of flash regeneration on MDEA solution is much better than MEAand PC solutions. Can be designed according to the principleTwo-stage absorption, one-stage normal-pressure desorption and one-stage steam regeneration process for reducing CO2The total heat energy consumption (total removal) is shown in figure two. Can also design an absorption-normal pressure desorption simple flow path to remove partial CO2(half-threshing) see figure three.
As seen from the first figure: the curve for MDEA lies between the chemical (MEA) and Physical (PC) absorption, and is therefore said to be absorbing CO2It has chemical and physical absorption properties or is called chemical and physical absorbent. But has the disadvantage of only being indirectly connected to CO2The reaction is also very slow.
2. Activator-1, p-diazacyclo (piperazine). It is a secondary amine, and the absorption of CO is greatly improved after the addition of it in MDEA solution2The reaction rate of (2). But its boiling point is low (148 deg.C), and it is easy to volatilize. And the addition concentration must not be too high, which would cause corrosion of the carbon steel. Furthermore, it has a low toxicity.
3. Activator-2, N-methyl-ethanolamine (MMEA). Is also a secondary amine, and its addition can also increase MDEA and CO2The speed of the reaction. The rate of increase was slightly lower for the same concentration added than for piperazine. And it is very effective for absorbing sulfur-oxygen-Carbon (COS).
4. Activator-3, Diethanolamine (DEA), which is also a secondary amine, the addition of which can accelerate both MEDA and CO2Besides the reaction speed, the surface CO of the MDEA solution is reduced2The effect of the partial pressure.
The three activators can be combined into the following groups of solutions: group A adds DEA (1+3) to diazacyclo; b group MMEA adds DEA (2+3), C group adds three groups of compound activators such as MMEA (1+2) to diazacyclo. Group A masterTo be administeredFor gases containing no organic sulfur, such as COS, etc., groups B and C for gases containing organic sulfur or CO for regenerated gas2Has special application. Experiments prove that the addition of the second activator not only can not offset the original activation effect in the MDEA solution, but also can play a mutual promotion role. The absorption speed of the composite activator is improved by about 10-20% compared with that of a single activator. In addition, the group A can reduce the content of the activator-1 to the diazacyclo, thereby reducing the loss caused by high steam partial pressure and the corrosion to the carbon steel caused by high concentration.
The structural formula of the N-methyldiethanolamine is as follows:
abbreviation R2CH3The reaction process of NN-methyldiethanolamine and carbon dioxide is as follows: ………………(2)(1)+(2) … … … (3) the whole reaction is controlled by (1), (1) is hydration reaction, at 25 deg.C, the reaction rate constant KOH is 104Liter/mol/sec. [ OH]]＝10-5～10-3Mols/liter. Therefore, the reaction (3) is a very slow reaction.
When adding activator secondary amine in MDEA solution, absorbing CO2The reaction of (3) was carried out according to the following scheme. …(5)(4)+(5)： ……(6)
Equation (6) is controlled by equation (4), where equation (4) is a two-stage reaction with a reaction rate constant KAm ═ 10 at 25 ℃4Liter/mol/sec. Free amine [ R]after addition of activator2′NH]＞10-2Mols/liter. It is thus seen that the reaction rate of reaction (4) is much faster than that of reaction (1).
In summary, the addition of the activator alters the absorption of CO by the MDEA solution2The course of (2). The activator plays a role in transferring CO2The function of (1). The reaction speed is accelerated. The activator absorbs CO on the surface2Then transferring CO to the liquid phase (MDEA solution)2And the activator is regenerated.
The desulfurization of the MDEA solution is carried out smoothly during the decarburization. The total sulfur in the raw material gas can be reduced to about 1 P.P.m.
The polyamine method solution of the invention comprises the following components by weight: group A: 20-60% of MDEA, 1-5% of piperazine, 1-10% of DEA, and B: 20-60% of MDEA, 0.1-10% of MMEA, 1-10% of DEA, C: 20-60% of MDEA, 1-5% of piperazine and 0.1-10% of MMEA.
The concentration of the solution actually used depends onthe composition of the gas to be treated, the degree of purification required and the pressure of the gas.
The comparative data of technical and economic indexes of the decarburization method of the invention and other decarburization methods are shown in table (1).
TABLE 1 comparison of technical and economic indicators for several decarburization processes
As seen from Table (1): the invention has regeneration heat consumption of 1881KJ/NM3CO2. About 1/2-1/3 of a composite catalytic method (CN851038557), although the absorption capacity of the invention is smaller than that of the composite catalytic method, the proportion of power consumption to total energy consumption is very small, so the total energy consumption is far smaller than that of the composite catalytic method.
The total stripping process flow adopted by the invention is shown in the second figure. Raw material gas entersThe bottom of the absorption tower 1 is contacted with polyamine absorption solution in countercurrent in the tower to remove CO in the gas2And sulfide, and the purified gas is led out from the top of the absorption tower 1 and sent to the next process through a cooler 6 and a separator 4. Containing CO from the bottom of the absorption tower 12The rich solution is decompressed and then enters an atmospheric pressure desorption tower 2, most of the desorbed semi-barren solution is pumped into the middle part of an absorption tower 1 by a semi-barren solution pump 11, a small amount of semi-barren solution is sent into a solution heat exchanger 9 by a relay pump 13 to obtain heat and then is sent to the top of a regeneration tower 3 to be subjected to steam stripping thermal regeneration, and the stripped steam is obtained by a boiler 10. The hot barren liquor from the bottom of the regeneration tower 3 is driven into a barren liquor cooler 7 by a barren liquor pump 12 after heat is recovered by a solution heat exchanger 9 and then enters the top of the absorption tower 1. The hot regeneration gas from the top of the regeneration tower 3 enters the bottom of the atmospheric desorption tower 2 to recover heat. The regenerated gas from the top of the atmospheric desorption tower 2 passes through a cooler 8 and a separator 5 and then is sent to the next process. Condensate separated from the purification gas separator 4 and the regeneration gas separator 5 is pumped into the top of the atmospheric desorption tower 2 by a condensate pump 14 so as to keep the water balance of the system.
The process flow of the invention can be carried out according to the process flow when a factory is newly built. If the invention is used in old factories which adopt the catalytic hot potash decarburization, the original process equipment can be properly modified. The upper tower of the original regeneration tower is changed into an atmospheric desorption tower, and the lower tower of the original regeneration tower is changed into the regeneration tower.
The semi-dehydration process flow adopted by the invention is shown in the third figure. The raw gas enters the bottom of the absorption tower 1, and the purified gas is led out from the top of the absorption towerThe cooler 2 and the separator 3 are sent to the next process. Containing CO from the bottom of the absorption tower 12The rich liquid is decompressed and then enters a normal pressure desorption tower 5 through a heater 4. The desorbed solution is pumped into the top of the absorption tower through a cooler 6 by a pump 9. The gas from the top of the atmospheric desorption tower 5 is sent to the next process or vented through a cooler 7 and a separator 8. The condensed water obtained from the separators 3 and 8 is pumped into the atmospheric desorption tower 5 by a pump 10.
The invention uses polyamine solution to remove CO2And the main process conditions of sulfide (total removal) are as follows:
operating pressure of the absorption tower: 1.3 to 3.0MPa (absolute)
Temperature of absorption tower barren solution: 50-75 DEG C
Temperature of absorption tower semi-barren solution: 75-90 DEG C
Tower kettle temperature of the regeneration tower: 100 to 115 DEG C
Raw material gas CO2The content is as follows: 17 to 30 percent
Total sulfur of raw material gas: 0 to 2000mg/NM3，
Total sulfur of purified gas: 1-3 P.P.m
Regenerated gas CO2The content is 98-99.8%
Solution absorption capacity: 13 to 25NM3CO2/M3Solutions of
Thermal energy consumption: 1881KJ/NM3CO2
(means Pco20.5MPa after the day)
H2·N2Loss: 15 to 25NM3/TNH3
Solvent loss: about 30g MDEA/TNH3
The invention uses polyamine solutions for partial CO removal2(semi-threshing) main workThe process conditions are as follows:
operating pressure of the absorption tower: 0.7 to 2.0MPa (absolute)
Temperature of absorption tower barren solution: 60-80 DEG C
Heater outlet solution temperature: 70-90 DEG C
Raw material gas CO2The content is as follows: 25 to 30 percent
Regenerated gas CO2The content is as follows: 96 to 99 percent
Solution absorption capacity: 7 to 16NM3CO2/M3Solutions of
H2、N2Loss: 15 to 25NM3/TNH3
Solvent loss: about 30g MDEA/TNH3
In conclusion, the invention has the advantages of high purification degree of the total-stripping process, low energy consumption of regenerative heat, stable solution, less loss, no corrosion of the solution to carbon steel equipment and no need of adding a preservative. The system equipment pipeline of the original catalytic hot potash can be utilized, and the solution can be replaced without great change, so that the energy consumption can be greatly saved. The economic benefit is very obvious.
Example 1
One-plant processing gas amount 5650NM3Industrial installation,/hr. Raw gas pressure 1.8MPa, CO content226.6% of total sulfur-430 mg/NM3. The solution B is decarbonized by the polyamine method. The purified gas contains CO20.1-0.2% and total sulfur less than or equal to 3 P.P.m. Regenerated gas CO2Not less than 99.8 percent. Thermal energy consumption 1881KJ/NM3CO2。H2、N2Loss 20NM3/TNH3. Solvent loss-30 g MDEA/TNH3。
Example 2
A plant for producing four million tons of urea for synthesizing ammonia in one year. The original method adopts benzene-Fischer method for decarburization. The treated gas amount is 17200NM3Hr, raw gas pressure of 1.45MPa, CO content229.4 percent. The purified gas contains CO20.2 to 0.3 percent. The thermal energy consumption is 6815KJ/NM2CO2(16.5T vapor/hr). And then, slightly modifying the device, replacing the solution, and decarbonizing by adopting the solution A. The purified gas contains CO20.1% or less. Regenerated gas CO2≥98.5％。H2，N2Loss 20NM2/TNH3. Thermal energy consumption 3139KJ/NM3CO2. The energy consumption is reduced by more than half compared with the original energy consumption.
Example 3
One-factory processing gas quantity 14000NM3Industrial installation,/hr. Raw gas pressure 1.4MPa, CO content229 percent. CO is carried out by using the solution B in the polyamine method2And partially removed (half removed). Purification of gas CO2-21%. Regenerated gas CO2More than or equal to 98 percent. Heat energy consumption 1045KJ/NM3CO2。H2、N2Loss 25NM3/TNH3。
Claims (1)
1. A polyamine method solution for removing carbon dioxide and sulfide in gas is characterized in that the solution comprises a composite activator formed by combining N-methyldiethanolamine solution and two secondary amines, and the solution components are respectively (weight concentration): group A, N-methyldiethanolamine 20-60%, piperazine 1-5%, and diethanolamine 1-10%; group B, N-methyldiethanolamine 20-60%, N-methyl monoethanolamine 0.1-10%, and diethanolamine 1-10%; group C, N-methyldiethanolamine 20-60%, piperazine 1-5%, and N-methyl monoethanolamine 0.1-10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93110579A CN1052430C (en) | 1993-02-25 | 1993-02-25 | Polyamine method for removing carbon dioxide and sulfide in gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93110579A CN1052430C (en) | 1993-02-25 | 1993-02-25 | Polyamine method for removing carbon dioxide and sulfide in gas |
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| CN1091332A CN1091332A (en) | 1994-08-31 |
| CN1052430C true CN1052430C (en) | 2000-05-17 |
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| CN93110579A Expired - Fee Related CN1052430C (en) | 1993-02-25 | 1993-02-25 | Polyamine method for removing carbon dioxide and sulfide in gas |
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| CN101786968B (en) * | 2009-01-23 | 2012-09-05 | 智胜化工股份有限公司 | Method for reducing decarburization energy consumption of N-Methyldiethanolamine (MDEA) |
| CN102049174A (en) * | 2009-10-28 | 2011-05-11 | 中国石油化工股份有限公司 | Method for partially separating carbon dioxide from gas mixture |
| CN101822932B (en) * | 2010-06-12 | 2013-01-02 | 中国石油集团工程设计有限责任公司 | Composite decarbonization solvent for eliminating carbon dioxide in natural gases |
| CN102423620B (en) * | 2011-10-26 | 2013-10-30 | 康达新能源设备股份有限公司 | Compound decarbonizing solvent for removing carbon dioxide from biogas |
| CN102989295A (en) * | 2012-11-23 | 2013-03-27 | 中国华能集团清洁能源技术研究院有限公司 | Absorbent which gathers carbon dioxide in flue gas or synthesis gas |
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| CN106831326A (en) * | 2016-12-22 | 2017-06-13 | 赛鼎工程有限公司 | A kind of comprehensive utilization process of coke-stove gas synthesizing methanol co-production liquefied natural gas |
| CN110624363B (en) * | 2019-09-12 | 2022-03-25 | 中国石油化工股份有限公司 | Pressurization regeneration method for capturing carbon dioxide in flue gas by alcohol amine method |
| CN114015486A (en) * | 2021-08-10 | 2022-02-08 | 陕西省石油化工研究设计院 | Activation synergist based on MDEA method natural gas decarbonization |
-
1993
- 1993-02-25 CN CN93110579A patent/CN1052430C/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 合成气脱二2碳技术经济评价 1992.1.1 化学工业部科学技术情报研究所 * |
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| CN1091332A (en) | 1994-08-31 |
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