CN102134519A - Combined process for natural gas desulfurization with high resource utilization ratio and good environmental protection effect - Google Patents
Combined process for natural gas desulfurization with high resource utilization ratio and good environmental protection effect Download PDFInfo
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- CN102134519A CN102134519A CN2010100231506A CN201010023150A CN102134519A CN 102134519 A CN102134519 A CN 102134519A CN 2010100231506 A CN2010100231506 A CN 2010100231506A CN 201010023150 A CN201010023150 A CN 201010023150A CN 102134519 A CN102134519 A CN 102134519A
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Abstract
The invention relates to a combined process for natural gas desulfurization with a high resource utilization ratio and a good environmental protection effect; natural gas is used as a raw material, and the process comprises the following steps: allowing the natural gas to entering a crude desulfurization unit which adopts a NHD physical absorption method for desulfurization so as to remove most sulfurs, then allowing the natural gas to entering a fine desulfurization unit for further desulfurization so as to allow the natural gas to meet the product requirements of downstream devices, allowing the tail gas of desulfurization in the crude desulfurization unit to enter firstly a COS transformation unit and a wet desulfurization unit so as to allow H2S to be transformed into elemental sulfurs for recovery, allowing the tail gas in the wet desulfurization unit to enter the fine desulfurization unit and then to enter a molecular sieve adsorption unit after desulfurization, recovering the methane gas in the tail gas, and removing CO2. Compared with the prior art, the invention has the advantages of high purification degree, obvious environmental protection effect, high resource utilization ratio, relatively low investment for device construction, low operation cost, etc.
Description
Technical field
The present invention relates to a kind of selexol process combination process, especially relate to the good selexol process combination process of a kind of resource utilization height and environment protecting.
Background technology
Marketable natural gas generally is meant the Sweet natural gas that comes out from gasser through after the preliminary desulfurization, total sulfur (comprising organosulfur, inorganic sulfur)≤200mg/m
3A kind of gas as commodity selling; marketable natural gas also will further remove sulphur according to the products production requirement before being converted into Chemicals usually; dry desulfurizing process is generally adopted in existing marketable natural gas desulfurization; as cobalt molybdenum hydrogenation catalyst sulfur removal technology, and dry method catalytic desulfurization technologies of coming out in the recent period newly developed.
Tradition cobalt molybdenum hydrogenation catalyst desulfurization process is roughly as follows: marketable natural gas is heated to about 380 ℃, mix with hydrogen, enter into cobalt molybdenum hydrogenation catalyst reactor then, with the sulphur compound hydrocrackings such as organosulfur in the marketable natural gas is hydrogen sulfide, then enter into the desulfurizer that zinc oxide is housed, make hydrogen sulfide and zinc oxide reaction in the Sweet natural gas generate zinc sulphide, to reach the purpose of removing sulphur, the Sweet natural gas that removes sulphur by the interchanger cooling after, gas is desulfurization finished product gas, if do not allow to contain hydrogen system, then enter dehydrogenation unit, remove hydrogen.
The technical process of typical case's dry method catalytic oxidation desulfurization is roughly as follows: considering the moisture deficit of Sweet natural gas, is again anaerobic state, so give moisturizing, oxygenation earlier.Will be after the oxygenating of marketable natural gas humidification by gas-liquid separator, reheat enters desulphurization system after 45～65 ℃ of the temperature of sweetening agent needs.Thionizer can adopt parallel connection or string and form, and Sweet natural gas enters in each thionizer, and each thionizer is equipped with catalytic desulfurizing agent, through behind the thionizer, makes the sulphur content in the Sweet natural gas reduce to specified requirement.The natural gas via strainer is removed the micro-dust that Sweet natural gas is carried secretly, gives downstream unit and uses, and all the other tail gas feed torch burning.This dry desulfurization process is a catalytic oxidation process, and oxygen is the essential reactant of this sulfur removal technology, and desulfurization product is elemental sulfur and high boiling point polysulfide.Therefore when using catalytic desulfurizing agent, must replenish a spot of oxygen (oxygen or air).Process flow diagram is seen Fig. 1.
Summary of the invention
Purpose of the present invention is exactly that a kind of degree of purification height, utilization ratio height, resource utilization height and the good selexol process combination process of environment protecting that running cost is low are provided in order to overcome the defective that above-mentioned prior art exists.
Purpose of the present invention can be achieved through the following technical solutions:
The selexol process combination process that a kind of resource utilization height and environment protecting are good is characterized in that, this technology may further comprise the steps:
(1) main sulfur removal technology: marketable natural gas enters thick desulfurization unit, and sulfide in the Sweet natural gas is by the NHD sweetening agent adsorbing and removing in the thick desulfurization unit, and the gas after removing enters smart desulfurization unit, through the COS hydrolysis, take off H
2After S and the mercaptan removal step, obtain removing the finished product Sweet natural gas of sulfide;
(2) vent gas treatment of thick desulfurization unit: the tail gas that produces in the thick desulfurization unit enters the COS conversion unit, and controlled temperature is 50 ℃～90 ℃, and COS is converted into H
2S, the H of generation
2S enters the wet desulphurization unit, and the effect by desulfurization catalyst is with H
2S is transformed into the elemental sulfur of suspension;
(3) the unitary vent gas treatment of wet desulphurization: the tail gas that produces in the wet desulphurization unit is through boosting to 1.5MPa～3.0MPa, enters the molecular sieve adsorption unit again after entering smart desulfurization unit desulfurization, and the methane gas that absorption obtains enters the finished product Sweet natural gas, the CO that removes
2Emptying.
Sulfide in the described step (1) in the Sweet natural gas comprises H
2S, COS, RSH and RSR.
NHD sweetening agent in the described step (1) is a Polyethylene glycol dimethyl ether.
Desulfurization catalyst in the described step (2) is a high-molecular complex, based on the 888 commercially available sweetening agents of three nuclear phthalocyanine cobalt sulfonate organometallicss.
The tail gas that produces in the wet desulphurization unit in the described step (3) comprises methane, CO
2And a small amount of sulphur component.
Described a small amount of sulphur component comprises H
2S, COS, RSH and RSR.
Smart desulfurization unit is identical with smart desulfurization unit in the step (1) in the described step (3).
Compared with prior art, the present invention has the following advantages:
(1) degree of purification height, environment protecting are obvious: in this process program owing to adopted technology such as NHD physical absorption desulfurization technology, COS technology for hydrolyzing, smart desulfurization and molecular sieve adsorption respectively, make the content of desulfurization purifying degree height, particularly organosulfur of Sweet natural gas further reduce.The tail gas that is rich in sulfide that produces in thick sulfur removal technology is through handling, the recyclable byproduct sulphur that obtains, make the quantity discharged of solid waste (particularly spent catalyst) greatly reduce, and traditional technology produces a large amount of zinc sulphide or sulfur-bearing and polysulfide solid waste, and environment protecting of the present invention is fairly obvious;
(2) resource utilization height: technical process of the present invention, make the sulfide of the interior overwhelming majority of marketable natural gas change into elemental sulfur, can be used as industrial chemicals is used, traditional technology then all is transformed into sulphur all in the marketable natural gas sulfur-containing solid refuse discharges, and also needs to consume a large amount of catalyzer simultaneously.It is main that technology main flow of the present invention adopts the physical absorption method, make the sulfide of the interior overwhelming majority of marketable natural gas be absorbed by NHD earlier, and have only the small portion marketable natural gas by catalyst layer, so the catalyst consumption amount is few.Traditional technology is then passed through catalyst layer with the entire service Sweet natural gas, so the catalyst consumption amount is very big.The wet desulphurization tail gas treatment process that technology of the present invention adopted has carried out abundant recovery to the methane gas in the tail gas, makes it to turn back to again in the main methane gas stream, and the methane of whole desulfurizer loses less than 0.1%, makes resource be able to sufficient utilization;
(3) Zhuan Zhi construction investment is relatively low, and the present invention is used for domestic a certain marketable natural gas desulfurizing item, about 1.1 hundred million yuans of its total investment for construction, and the dry desulfurizing process of common catalytic desulfurizing agent, about 1.4 hundred million yuans of its total investment for construction;
(4) running cost is low, and the running cost of sulfur removal technology of the present invention is starkly lower than the cost of dry desulfurizing process.
Description of drawings
Fig. 1 is a dry method catalytic oxidation desulfurization technology general flow chart in parallel;
Fig. 2 is a process flow sheet of the present invention.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Embodiment
Domestic a certain marketable natural gas desulfurizing item
Scale: handle Sweet natural gas tolerance 215000Nm
3/ hr
Sweet natural gas composition and temperature, pressure see Table 1.
Table 1
| Composition | Unit | Specification |
| Methane | Vol.％ | 97.06 |
| Ethane | Vol.％ | 0.15 |
| Propane | Vol.％ | 0.01 |
| N 2 | Vol.％ | 0.71 |
| O 2 | Vol.％ | -- |
| Helium | Vol.％ | 0.01 |
| Hydrogen | Vol.％ | 0.03 |
| CO 2 | Vol.％ | 2.03 |
| COS | mg?S/Nm 3 | |
| Organosulfur | mg?S/Nm 3 | |
| Sulfur-bearing composition (in S) | mg?S/Nm 3 | Total sulfur≤200mg/Nm 3Wherein: H 2S≤20mg/Nm 3COS 〉=70% organosulfur (RSH, R-S-R)≤20% |
| H 2O | Vol.％ | 0.004 |
| Mechanical impurity size＜50 μ m | mg/Nm 3 | |
| Low heat value | MJ/Nm 3(dry) | |
| Pressure | MPa(g) | 3.6～4 |
| Temperature | ℃ | -4.5～13℃ |
Processing parameter and desulfurization requirement
(1) total sulfur (in S) :≤0.3mg/Nm
3
(2) must not use brass work in the sweetening process;
(3) sweetening process does not add hydrogen;
(4) year operating time: 8000h;
(5) pressure after the desulfurization is 0.7～0.9MPa (g);
(6) temperature is 40 ℃.
The selexol process combination process that a kind of resource utilization height and environment protecting are good, process diagram as shown in Figure 2, this technology may further comprise the steps:
(1) main desulfurization process
Raw natural gas (215000Nm
3/ hr) entering thick, smart desulfurization unit, the sulfide in the Sweet natural gas comprises H
2S, COS, RSH and RSR.Wet method NHD physical absorption sulfur removal technology is adopted in thick desulfurization, and the NHD sweetening agent is a Polyethylene glycol dimethyl ether, NHD desulfurization lean solution counter current contact on filler that raw natural gas and thionizer top enter, wherein most H
2S, COS, sulfide is by physical absorption, CO
2Gas is partially absorbed.Thick desulfurization can be with the total sulfur 200mg/Nm in the raw material
3Be removed to 8mg/Nm
3, the methane gas that goes out thick desulfurization unit enters the smart desulfurization unit of dry method, catalyzer is housed (with r-AL in the smart desulfurization unit
2O
3Add Mo, Ti, Mn, Ni or/and the r-AL of the water-soluble cpds of any metal among K, Na, Ca, the Mg with mixed grind method or pickling process
2O
3, it is r-AL that the amount of metal of adding is converted into metal oxide
2O
30.001%～20% of quality, drying or the oven dry roasting make), sweetening agent (special typed active carbon), COS becomes H through the catalyzer hydrolysis
2S removes H through sweetening agent again
2S and mercaptan are removed to remaining sulphur and satisfy total sulfur≤0.3mg/Nm
3Requirement, the methane gas methane gas with tail gas recycle behind the puffing recovered energy that goes out smart desulfurization unit enters downstream unit.The sulfur compound NHD rich solution of discharging at the bottom of thick desulfurization unit thionizer enters flash drum and carries out flash distillation after decompression, reclaim methane gas, enters regenerator column after the rich solution heat exchange and carries out heat regeneration, enters thionizer after regenerated liquid pressurizes, cools off and carries out recycle.
(2) treatment scheme of thick desulfidation tail gas
The rich sulphur tail gas and the about 6100Nm of flash steam of thick desulfurization unit
3/ hr enters the COS conversion unit through boosting, controlled temperature is 50 ℃～90 ℃, makes COS be converted into H
2S then enters wet method and takes off H
2The S unit is rich in H
2The tail gas of S in thionizer with contain the alkali lye counter current contact of sweetening agent, to remove the hydrogen sulfide in the tail gas, the desulfurization catalyst that is adopted is a high-molecular complex, promptly based on the 888 commercially available sweetening agents of three nuclear phthalocyanine cobalt sulfonate organometallicss, its specific molecule structure makes it have very strong ability to take oxygen, and the oxygen of absorption can be activated.Simultaneously can adsorb H
2S, HS
-, Sx
2-And be adsorbed the oxygen that has activated and carry out redox reaction and separate out sulphur; after the elemental sulfur that generates breaks away from sweetening agent; small sulfur granules combination adjacent to each other in solution; become suspension sulphur and enter the rich solution groove from the desulfurization rich solution that thionizer comes out; by being sent to jet regeneration tank regeneration after the pressurization of rich solution pump, the sulphur foam that floatingly selects advances people's sulphur foam chute and is sent to sulfur recovery system, obtains the solid sulfur byproduct through molten sulphur.The desulfurization lean solution that regeneration is good is sent to the desulfurization cat head and recycles, and the tail gas after wet desulphurization enters the wet desulphurization tail gas treating unit.
(3) wet desulphurization vent gas treatment flow process
The tail gas that produces in the wet desulphurization unit enters the smart desulfurization unit of tail gas through boosting to 1.5MPa～3.0MPa, and tail gas comprises methane, CO
2And small amount of H
2S, COS, RSH, RSR, flow process is identical with smart desulfurization unit in the main sulfur removal technology, but the scale difference, through further entering the molecular sieve adsorption unit after the desulfurization, adopts molecular sieve adsorption to reclaim wherein the about 5058Nm of methane gas
3/ h, the methane gas stream after the smart desulfurization of this methane gas in main desulfurization process enters downstream unit after mixing.Remove most of CO simultaneously in the molecular sieve adsorption unit
2Gas makes CO
2Emptying up to standard.
Claims (7)
1. resource utilization height and the good selexol process combination process of environment protecting is characterized in that this technology may further comprise the steps:
(1) main sulfur removal technology: marketable natural gas enters thick desulfurization unit, and sulfide in the Sweet natural gas is by the NHD sweetening agent adsorbing and removing in the thick desulfurization unit, and the gas after removing enters smart desulfurization unit, through the COS hydrolysis, take off H
2After S and the mercaptan removal step, obtain removing the finished product Sweet natural gas of sulfide;
(2) vent gas treatment of thick desulfurization unit: the tail gas that produces in the thick desulfurization unit enters the COS conversion unit, and controlled temperature is 50 ℃～90 ℃, and COS is converted into H
2S, the H of generation
2S enters the wet desulphurization unit, and the effect by desulfurization catalyst is with H
2S is transformed into the elemental sulfur of suspension;
(3) the unitary vent gas treatment of wet desulphurization: the tail gas that produces in the wet desulphurization unit is through boosting to 1.5MPa～3.0MPa, enters the molecular sieve adsorption unit again after entering smart desulfurization unit desulfurization, and the methane gas that absorption obtains enters the finished product Sweet natural gas, the CO that removes
2Emptying.
2. a kind of resource utilization height according to claim 1 and the good selexol process combination process of environment protecting is characterized in that, the sulfide in the described step (1) in the Sweet natural gas comprises H
2S, COS, RSH and RSR.
3. a kind of resource utilization height according to claim 1 and the good selexol process combination process of environment protecting is characterized in that the NHD sweetening agent in the described step (1) is a Polyethylene glycol dimethyl ether.
4. a kind of resource utilization height according to claim 1 and the good selexol process combination process of environment protecting, it is characterized in that, desulfurization catalyst in the described step (2) is a high-molecular complex, based on the 888 commercially available sweetening agents of three nuclear phthalocyanine cobalt sulfonate organometallicss.
5. a kind of resource utilization height according to claim 1 and the good selexol process combination process of environment protecting is characterized in that, the tail gas that produces in the wet desulphurization unit in the described step (3) comprises methane, CO
2And a small amount of sulphur component.
6. a kind of resource utilization height according to claim 5 and the good selexol process combination process of environment protecting is characterized in that described a small amount of sulphur component comprises H
2S, COS, RSH and RSR.
7. a kind of resource utilization height according to claim 1 and the good selexol process combination process of environment protecting is characterized in that, smart desulfurization unit is identical with smart desulfurization unit in the step (1) in the described step (3).
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Cited By (10)
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| CN103013600A (en) * | 2012-11-19 | 2013-04-03 | 河南天冠工业沼气有限公司 | Biogas desulfurization method in series of wet method with dry method |
| CN103242923A (en) * | 2013-04-15 | 2013-08-14 | 利丰工程技术(天津)有限公司 | Natural gas desulfurization device and desulfurization process applicable to production platform |
| CN103446861A (en) * | 2013-09-13 | 2013-12-18 | 四川鸿鹄科技集团有限公司 | Circulating treatment method for regenerated waste gas produced in temperature swing adsorption desulfurization |
| CN104437032A (en) * | 2014-11-11 | 2015-03-25 | 浙江三龙催化剂有限公司 | Synthetic raw material gas deep fine desulfurization process and fine desulfurization device |
| CN105032157A (en) * | 2015-09-06 | 2015-11-11 | 中国五环工程有限公司 | Amine liquid desulphurization technology and device for removing hydrogen sulfide and carbonyl sulfide in acid gas |
| CN106190386A (en) * | 2016-08-26 | 2016-12-07 | 成都巨涛油气工程有限公司 | A kind of method of deep natural gas removing organic sulfur |
| CN107970754A (en) * | 2018-01-15 | 2018-05-01 | 青海盐湖工业股份有限公司 | The reuse means and reuse method of a kind of calcium carbide stove exhaust |
| CN108993133A (en) * | 2017-06-06 | 2018-12-14 | 中国石油化工股份有限公司 | COS, CS in a kind of promotion natural gas2The method of removing |
| CN111321015A (en) * | 2020-03-12 | 2020-06-23 | 中国科学院过程工程研究所 | Blast furnace gas dry desulfurization and sulfur recycling device |
| CN115155273A (en) * | 2022-08-08 | 2022-10-11 | 东营职业学院 | Integrated food-grade and industrial-grade carbon dioxide recovery device and recovery process |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103013600A (en) * | 2012-11-19 | 2013-04-03 | 河南天冠工业沼气有限公司 | Biogas desulfurization method in series of wet method with dry method |
| CN103242923A (en) * | 2013-04-15 | 2013-08-14 | 利丰工程技术(天津)有限公司 | Natural gas desulfurization device and desulfurization process applicable to production platform |
| CN103446861A (en) * | 2013-09-13 | 2013-12-18 | 四川鸿鹄科技集团有限公司 | Circulating treatment method for regenerated waste gas produced in temperature swing adsorption desulfurization |
| CN104437032A (en) * | 2014-11-11 | 2015-03-25 | 浙江三龙催化剂有限公司 | Synthetic raw material gas deep fine desulfurization process and fine desulfurization device |
| CN105032157A (en) * | 2015-09-06 | 2015-11-11 | 中国五环工程有限公司 | Amine liquid desulphurization technology and device for removing hydrogen sulfide and carbonyl sulfide in acid gas |
| CN106190386B (en) * | 2016-08-26 | 2022-05-24 | 四川鸿鹄科技集团有限公司 | Method for deeply removing organic sulfur from natural gas |
| CN106190386A (en) * | 2016-08-26 | 2016-12-07 | 成都巨涛油气工程有限公司 | A kind of method of deep natural gas removing organic sulfur |
| CN108993133A (en) * | 2017-06-06 | 2018-12-14 | 中国石油化工股份有限公司 | COS, CS in a kind of promotion natural gas2The method of removing |
| CN107970754A (en) * | 2018-01-15 | 2018-05-01 | 青海盐湖工业股份有限公司 | The reuse means and reuse method of a kind of calcium carbide stove exhaust |
| CN111321015B (en) * | 2020-03-12 | 2021-06-04 | 中国科学院过程工程研究所 | Blast furnace gas dry desulfurization and sulfur recycling device |
| CN111321015A (en) * | 2020-03-12 | 2020-06-23 | 中国科学院过程工程研究所 | Blast furnace gas dry desulfurization and sulfur recycling device |
| CN115155273A (en) * | 2022-08-08 | 2022-10-11 | 东营职业学院 | Integrated food-grade and industrial-grade carbon dioxide recovery device and recovery process |
| CN115155273B (en) * | 2022-08-08 | 2023-08-22 | 东营职业学院 | Integrated food-grade and industrial-grade carbon dioxide recovery device and recovery process |
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Address after: 200032, 807 Jia Jia Road, Shanghai Patentee after: SHANGHAI HUANQIU ENGINEERING CO., LTD. Address before: 200032, Shanghai, Xuhui District Jia Bang Road, No. 807 Patentee before: Shanghai Huanqiu Petrochemistry Engineering Co., Ltd. |