CN102732349A - Method for producing liquefied natural gas - Google Patents
Method for producing liquefied natural gas Download PDFInfo
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- CN102732349A CN102732349A CN2012102513436A CN201210251343A CN102732349A CN 102732349 A CN102732349 A CN 102732349A CN 2012102513436 A CN2012102513436 A CN 2012102513436A CN 201210251343 A CN201210251343 A CN 201210251343A CN 102732349 A CN102732349 A CN 102732349A
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Abstract
The invention discloses a method for producing liquefied natural gas. The method comprises the following steps of: (1) compressing and preheating virgin gas, and then deoxidizing to obtain deoxidized virgin gas; (2) introducing the deoxidized virgin gas into a purifying unit I to remove acid gas to obtain purified gas; (3) introducing the purified gas into a natural synthesis unit to react with methane to obtain crude synthesis gas; (4) introducing the crude synthesis gas into a purifying unit II for decarbonizing to obtain purified synthesis gas; (5) introducing the purified synthesis gas into a natural gas refining unit to remove H2O and CO2 to obtain nitrogen-rich natural gas; and (6) introducing the nitrogen-rich natural gas into a natural gas liquefying and separating unit for cooling and separating to obtain the liquefied natural gas. In the invention, low-heat-value blue carbon gas is converted into high-added-value clean fuel LNG (Liquefied Natural Gas) by adopting an advanced and reliable process technology, so the method has active effects on saving energy, reducing emission and protecting environment, conforms to the requirements of national industrial policies and environmental protection policies, enables enterprises to obtain considerable economic benefit and opens a new approach for the reasonable utilization of the blue carbon gas.
Description
Technical field
The present invention relates to a kind of method of producing natural gas liquids, belong to technical field of chemical synthesis.
Background technology
In the process of producing blue charcoal, produce a large amount of blue charcoal tail gas, according to the difference of ature of coal, one ton of blue charcoal of every production (also claiming the coal semicoke) will produce blue charcoal tail gas 600 ~ 1000Nm
3About, calorific value 1700-2200kcal, with respect to coke oven tail gas and coal-seam gas etc., blue charcoal tail gas is the lower thermal source of a kind of quality, the unit volume gas heating value is relatively low.The directly emptying burning of the basic overwhelming majority of present blue charcoal tail gas only has the sub-fraction utilization, contains a large amount of H in the tail gas
2, CH
4, available gas composition such as CO, be a kind of good gas energy, but blue charcoal tail gas also contains obnoxious flavour and rare gas elementes such as hydrogen sulfide and carbonic acid gas simultaneously, directly burning or effluxing all is prone to cause environmental pollution.So this part blue charcoal tail gas not only causes huge energy dissipation if can not rationally utilize, and have a strong impact on the local ecotope of factory.The present mode of utilizing of blue charcoal tail gas mainly is a combustion power generation, accounts for 30% of exhaust emissions total amount, and added value is relatively low.
2011, national blue charcoal industrial scale was 4,800 ten thousand tons/year, and manufacturing enterprise mainly concentrates on areas such as Shanxi, Shaanxi, the Inner Mongol, Ningxia, has formed the development pattern of mass-producing.The industrial scale that expects blue charcoal in 2015 can reach 6,000 ten thousand tons/year, can produce more than tail gas 400 billion cubic meters.Utilize blue charcoal tail gas how rationally, efficiently, when solving environmental problem, creating higher economic benefit becomes the new developing direction of industry.
Summary of the invention
The purpose of this invention is to provide a kind of method of producing natural gas liquids,, can make enterprise obtain considerable economic simultaneously again, opened up new thinking for the reasonable utilization of waste gas such as blue charcoal tail gas to solve the environmental problem that exhaust emissions causes.
A kind of method of producing natural gas liquids provided by the present invention comprises the steps:
(1) virgin gas carries out deoxygenation and obtains the deoxygenation virgin gas after compression and preheating;
(2) said deoxygenation virgin gas enters to clean unit I and carries out removing of sour gas and be purified gas;
(3) said purified gas enters to the Sweet natural gas synthesis unit and obtains crude synthesis gas through methanation reaction;
(4) said crude synthesis gas enters to clean unit II and is purified synthetic gas through decarburization;
(5) said purification synthetic gas enters to the natural gas fine purification unit through removing H
2O and CO
2After obtain rich nitrogen Sweet natural gas;
(6) said rich nitrogen Sweet natural gas enters to the natural gas liquefaction separating unit and promptly gets natural gas liquids through refrigerated separation.
In the above-mentioned method, said virgin gas specifically can be waste gas such as blue charcoal tail gas, coke-oven gas, coal-seam gas or calcium carbide tail gas.
In the above-mentioned method, in the step (1), said virgin gas is compressed to 2MPa ~ 5MPa, sending into deaerator after being preheated to 180 ℃ ~ 260 ℃ carries out deoxygenation.
In the above-mentioned method, in the step (1), remove the oxygen in the said virgin gas through the hydrogenation catalyst oxidizing reaction, the purpose of said deoxygenation is to blast for fear of subsequent technique, also is in order to protect methanation catalyst simultaneously.
In the above-mentioned method, in the step (2), said clean unit I removes the sour gas in the said deoxygenation virgin gas through the physical absorption method; The solvent of said physical absorption method is a methyl alcohol; CO in the purified gas in the said purified gas after removing sour gas
2Content is less than 3% (vol), H
2S+COS<0.1ppm.
In the above-mentioned method, in the step (3), said methanation reaction can carry out in methanator; Said methane reactor comprises first stage reactor and second stage reactor.
In the above-mentioned method, in the step (4), said clean unit II removes the CO in the said crude synthesis gas through the physical absorption method
2The solvent of said physical absorption method is a methyl alcohol, is used for washing and absorbs CO
2, make CO wherein
2Content is lower than 50ppm.
In the above-mentioned method, in the step (5), said natural gas fine purification unit adopts sieve adsorpting bed to remove H
2O and CO
2, for satisfying the requirement of low-temperature working state, water-content is lower than 1ppm in the rich nitrogen Sweet natural gas after said sieve adsorpting bed refining with adsorbents.
In the above-mentioned method, in the step (6), said natural gas liquefaction separating unit is through deep cooling low temperature separating methods separation of nitrogen and natural gas liquids; Utilize the rerum natura difference of nitrogen and methane; Through rectifying nitrogen is separated from rich nitrogen Sweet natural gas, and reclaim the cold in the nitrogen re-heat process, for natural gas liquefaction provides cold; Reduced the energy consumption of whole process flow, wherein said deep cooling low temperature separating methods adopts azeotrope refrigeration cycle (MCR).
The present invention has following advantage:
1, the purifying method that the present invention adopted belongs to maturation process mostly, the industriallization good reliability;
2, it is complicated to have solved exhaust gas constituents such as blue charcoal tail gas, the difficult problem that a nitrogen content is high, calorific value is low;
3, make full use of blue charcoal tail gas, not only solved environmental issue but also produced good economic benefit;
Method provided by the invention is all cooled off nitrogen and synthetic natural gas at the natural gas liquefaction separating unit; Utilize the rerum natura difference of nitrogen and methane then; Through rectifying nitrogen is separated from rich nitrogen Sweet natural gas; And reclaim the cold in the nitrogen re-heat process, for natural gas liquefaction provides cold, reduced the energy consumption of whole process flow.Adopt advanced, reliable Technology low-calorie blue charcoal tail gas to be converted into the clean fuel LNG of high added value; To bring into play positive effect for energy-saving and emission-reduction, protection environment; Meet the requirement of national industrial policies and environmental protection policy; Can make simultaneously enterprise obtain considerable economic again, open up a new thinking for the reasonable utilization of blue charcoal tail gas.
Description of drawings
Fig. 1 is the schematic flow sheet of method provided by the invention;
Fig. 2 is the schematic flow sheet of the purification process in the method provided by the invention;
Fig. 3 is the schematic flow sheet of the Sweet natural gas synthesis technique in the method provided by the invention;
Fig. 4 is natural gas fine purification and the schematic flow sheet of liquefying separation process in the method provided by the invention.
Embodiment
Employed experimental technique is ordinary method like no specified otherwise among the following embodiment.
Used material, reagent etc. like no specified otherwise, all can obtain from commercial sources among the following embodiment.
The schematic flow sheet of present embodiment production natural gas liquids is as shown in Figure 1.
Blue charcoal tail gas virgin gas is formed as shown in table 1:
The blue charcoal tail gas of table 1 is on average formed (vol%)
Wherein: Lower heat value: 8187kJ/Nm
3(1987kcal/Nm
3); Temperature: 40 ℃; Pressure: 0.03MPa (G).
Flow process is following:
(1) deoxygenation unit
Blue charcoal tail gas from gas holder is compressed to 2.5MPa (G) through feed gas compressor, be preheated to 200 ~ 240 ℃ by crude synthesis gas after, get into the deoxygenation groove, remove the oxygen in the virgin gas through the hydrogenation catalyst oxidizing reaction.Emit big calorimetric in the process of deoxidation, the virgin gas after the intensification after virgin gas finally is cooled to 40 ℃, is delivered to clean unit I after virgin gas enters the mouth preheater, Low Pressure Waste Heat Boiler, de-salted water preheater recovery heat.
(2) clean unit I
This clean unit I comprises absorption and regeneration, and is as shown in Figure 2.
Absorb: the deoxygenation virgin gas is removed in Ammonic washing tower through washing step, and the phenol that trace exists is with eccysis from virgin gas simultaneously.Virgin gas after the prewashing gets into the H on absorption tower
2The S absorber portion in this section, is used from CO
2The no sulphur methyl alcohol rich solution spray washing that absorber portion gets removes the H in the raw gas
2S and COS sulfides.Virgin gas after the desulfurization is by H
2Back entering CO comes out at S absorber portion top
2The absorber portion bottom.Remove CO
2The back goes out the absorption tower at-49 ℃, then through the rich solution water cooler, removes the methane synthesis unit after the feed gas chiller re-heat.CO in the purified gas
2Content is less than 3% (vol), H
2S+COS<0.1ppm; Get into the Sweet natural gas synthesis unit then.
The regeneration of solution: the methyl alcohol rich solution that produces from methyl alcohol flasher bottom gets into H
2The S upgrading tower carries out the flash distillation stripping.The methyl alcohol rich solution adopts the low-pressure nitrogen stripping, and the nitrogen that adds at the bottom of the tower is with CO
2Stripping goes out cat head, then after gas is carried nitrogen cooler recovery cold, as the emptying of the high point of tail gas.Rich H
2The S methanol solution is from H
2The laggard hot regenerator column feeding pump pressurization of coming out at the bottom of the S upgrading tower, the heat exchange of the methyl alcohol lean solution water cooler into Mathanol regenerating top of tower that heats up.Remaining CO in the methyl alcohol
2And dissolved H
2The heat that S is provided by reboiler carries out heat regeneration, and mixed air goes out cat head through multistage refrigerated separation, and methyl alcohol one-level phlegma refluxes, and B-grade condensation liquid gets into H through heat exchange
2S upgrading tower bottom.The methyl alcohol of holomorphosis is delivered to the top, absorption tower after cooling.
(3) Sweet natural gas synthesis unit
As shown in Figure 3; Self-purification unit I through the purified gas behind the acid gas removal earlier through recycle gas cooler and circulation gas heat exchange, after the heat exchange of wet body is preheated to 320 ℃ in feed gas heater and second stage reactor export; Send into desulfurizer and remove trace hydrogen sulfide; Purify conversion gas and heating cycle gas and be mixed into the methanation first stage reactor, after first stage reactor outlet high-temperature gas reclaimed heat through vapor superheater, vapour generator, a part was returned and is made first stage reactor inlet circulation gas; A part is as second stage reactor inlet virgin gas, and circulating flow rate is confirmed by the first stage reactor Outlet Gas Temperature.High temperature circulation gas at first passes through the heat exchange of circulation gas interchanger with compression back cold cycle gas, reclaims heat through recycle gas cooler again, and the most laggard recycle gas compressor compresses.Behind the wet body preheating material gas, be cooled to 40 ℃ through water cooler again in the second stage reactor outlet, carry out gas-liquid separation, dirt gas is delivered to clean unit II.
(4) clean unit II
As shown in Figure 2, clean unit II will remove unreacted CO in the crude synthesis gas of the synthetic back of Sweet natural gas
2Crude synthesis gas from the Sweet natural gas synthesis unit gets into clean unit II through the crude synthesis gas separator, absorbs the lower concentration CO in the thick synthetic natural gas earlier through poor first
2, with the CO in the synthetic gas
2Content is reduced to 50ppm.℃ go into from the jacking of methyl alcohol absorption tower through refrigerative methyl alcohol-49 from the Mathanol regenerating tower, the absorption tower epimere is CO
2Absorber portion, methanol solution contacts with back flow of gas from top to bottom, removes CO in the gas
2, the hypomere on the absorption tower, the methanol solution of drawing get into the methyl alcohol flasher, deliver to the methane synthesis unit after the gas pressurization that flashes off from the methyl alcohol flash drum, to reclaim H
2And CO.
Identical among the regeneration of clean unit II solution and the clean unit I.
(5) natural gas fine purification unit
As shown in Figure 4, the purification synthetic gas that self-purification unit II comes passes sieve adsorpting bed, removes micro-H
2O, CO
2After obtain rich nitrogen Sweet natural gas, send into the natural gas liquefaction separating unit.Sieve adsorpting bed is two switch to be used, an absorption, thermal regeneration, cold blowing.For satisfying the requirement of low-temperature working state, water-content is lower than 1ppm in the rich nitrogen Sweet natural gas after sieve adsorpting bed is refining.
(6) natural gas liquefaction separating unit
As shown in Figure 4; Rich nitrogen natural gas via compression is pressurized to main heat exchanger and azeotrope (azeotrope comprises nitrogen, iso-pentane, ethene and the propane) heat exchange that enters into the natural gas liquefaction separating unit behind the 5.0MPa; Be cooled to draw after the certain temperature vaporizer that interchanger enters into rectifying tower and continued to cool off the back and get into rectifying tower and carry out rectifying, the LNG at the bottom of the tower is heated evaporation in vaporizer simultaneously; Divide two-way from the cat head separated nitrogen; One the tunnel after board-like re-heat the additional nitrogen as system use; Another road is distillated after the condenser condenses of cat head as the phegma of rectifying tower, and azeotrope gets into condensing surface as the liquefaction of nitrogen of low-temperature receiver with rectifying tower top through main heat exchanger cooling throttling rear section simultaneously.The natural gas liquids that rectifier bottoms fractionates out continues to turn back in the main heat exchanger by cold excessively, and throttling is depressured to storage pressure behind the cooling box, sends into the LNG storage tank at last.
According to schematic flow sheet Fig. 1, each logistics data is as shown in table 2:
Table 2 is produced the composition of each logistics in the natural gas liquids process
Claims (10)
1. a method of producing natural gas liquids comprises the steps:
(1) virgin gas carries out deoxygenation and obtains the deoxygenation virgin gas after compression and preheating;
(2) said deoxygenation virgin gas enters to clean unit I and carries out removing of sour gas and be purified gas;
(3) said purified gas enters to the Sweet natural gas synthesis unit and obtains crude synthesis gas through methanation reaction;
(4) said crude synthesis gas enters to clean unit II and is purified synthetic gas through decarburization;
(5) said purification synthetic gas enters to the natural gas fine purification unit through removing H
2O and CO
2After obtain rich nitrogen Sweet natural gas;
(6) said rich nitrogen Sweet natural gas enters to the natural gas liquefaction separating unit and promptly gets natural gas liquids through refrigerated separation.
2. method according to claim 1 is characterized in that: said virgin gas is blue charcoal tail gas, coke-oven gas, coal-seam gas or calcium carbide tail gas.
3. method according to claim 1 and 2 is characterized in that: in the step (1), said virgin gas is compressed to 2MPa ~ 5MPa, be preheated to 180 ℃ ~ 260 ℃.
4. according to arbitrary described method among the claim 1-3, it is characterized in that: in the step (1), remove the oxygen in the said virgin gas through the hydrogenation catalyst oxidizing reaction.
5. according to arbitrary described method among the claim 1-4, it is characterized in that: in the step (2), said clean unit I removes the sour gas in the said deoxygenation virgin gas through the physical absorption method; The solvent of said physical absorption method is a methyl alcohol.
6. according to arbitrary described method among the claim 1-5, it is characterized in that: in the step (3), said methanation reaction carries out in methanator; Said methane reactor comprises first stage reactor and second stage reactor.
7. according to arbitrary described method among the claim 1-6, it is characterized in that: in the step (4), said clean unit II removes the CO in the said crude synthesis gas through the physical absorption method
2The solvent of said physical absorption method is a methyl alcohol.
8. according to arbitrary described method among the claim 1-7, it is characterized in that: in the step (5), said natural gas fine purification unit adopts sieve adsorpting bed to remove H
2O and CO
2
9. according to arbitrary described method among the claim 1-8, it is characterized in that: in the step (6), said natural gas liquefaction separating unit is through deep cooling low temperature separating methods separation of nitrogen and natural gas liquids.
10. method according to claim 9 is characterized in that: said deep cooling low temperature separating methods adopts the azeotrope refrigeration cycle.
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CN104388139A (en) * | 2014-11-11 | 2015-03-04 | 上海鑫兴化工科技有限公司 | Direct methanation method and system for raw coal gas |
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CN105992632A (en) * | 2014-04-09 | 2016-10-05 | 埃克森美孚上游研究公司 | Methods and systems for purifying natural gases |
CN104017620A (en) * | 2014-05-20 | 2014-09-03 | 榆林科大高新能源研究院有限公司 | Process method for co-production of liquid ammonia and liquefied natural gas by using carbonized furnace gas |
CN104017620B (en) * | 2014-05-20 | 2016-04-13 | 榆林科大高新能源研究院有限公司 | The processing method of charing furnace gas liquefied ammonia co-production of liquefied Sweet natural gas |
CN104119973A (en) * | 2014-08-13 | 2014-10-29 | 新地能源工程技术有限公司 | Method for preparing natural gas from coal-bed gas |
CN104388139A (en) * | 2014-11-11 | 2015-03-04 | 上海鑫兴化工科技有限公司 | Direct methanation method and system for raw coal gas |
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CN106566566A (en) * | 2015-10-10 | 2017-04-19 | 中国石油化工股份有限公司 | Methanation method of oxygen-containing raw material |
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CN106268164A (en) * | 2016-08-25 | 2017-01-04 | 中国天辰工程有限公司 | A kind of coupling decarbonization process of coal preparing liquefied natural gas |
CN107042051A (en) * | 2017-01-10 | 2017-08-15 | 杨皓 | Preliminary clearning prevents frozen block technique before a kind of methanation LNG liquefaction |
CN109099641A (en) * | 2017-09-13 | 2018-12-28 | 北京恒泰洁能科技有限公司 | A kind of cryogenic separation system and method recycling tail of semi coke |
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Application publication date: 20121017 |