CN207596802U - A kind of system by calcium carbide stove exhaust production liquefied natural gas - Google Patents
A kind of system by calcium carbide stove exhaust production liquefied natural gas Download PDFInfo
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- CN207596802U CN207596802U CN201721003006.XU CN201721003006U CN207596802U CN 207596802 U CN207596802 U CN 207596802U CN 201721003006 U CN201721003006 U CN 201721003006U CN 207596802 U CN207596802 U CN 207596802U
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Abstract
The utility model is related to a kind of systems by calcium carbide stove exhaust production liquefied natural gas, the system includes sequentially connected dust-extraction unit, gas holder, the first compressor, first cleaning system, the second compressor, heat exchanger, change furnace, fine de-sulfur system, methane synthesis reaction system, NHD decarbonizing towers, MDEA decarbonizing towers, dehydration device, natural gas liquefaction system, and the entrance of the dust-extraction unit is connected with calcium carbide stove exhaust feed pipe.The system of the utility model has many advantages, such as calcium carbide stove exhaust utilization rate of active components height, and product meets subsequent technique requirement.
Description
Technical field
The utility model is related to a kind of systems by calcium carbide stove exhaust production liquefied natural gas.
Background technology
At present, the calcium carbide stove exhaust that diffuses or ignite the torch is more than 150 billion cubic meters every year for China, calcium carbide stove exhaust mainly into
Part it is：CO 70~90%, H22.5~10%, CH42~4%, N21~2%, CO22.5~3.5%, O20.2~
0.6%, it diffuses or ignites the torch and not only waste mass energy, also result in environmental pollution.Calcium carbide stove exhaust production LNG techniques are developed,
Not only calcium carbide stove exhaust is made efficiently to utilize, but also calcium carbide industry New Ideas of Developing can be expanded, be that current calcium carbide industry develops urgently
It solves the problems, such as.
Chinese patent 201210251343.6 discloses a kind of method for producing liquefied natural gas, includes the following steps：(1)
Unstripped gas is compressed to obtain deoxygenation unstripped gas with progress deoxygenation after preheating；(2) the deoxygenation unstripped gas enter to clean unit I into
The removing of row sour gas is purified gas；(3) purified gas enters to natural gas synthesis unit and is obtained through methanation reaction
Crude synthesis gas；(4) crude synthesis gas enters to clean unit II and is purified synthesis gas through decarburization；(5) the purification synthesis
Gas enters to natural gas fine purification unit through removing H2O and CO2After obtain rich nitrogen natural gas；(6) the rich nitrogen natural gas enters to day
Right gas liquefaction separative element is through refrigerated separation up to liquefied natural gas.In above-mentioned method, the unstripped gas concretely semi-coke
The exhaust gas such as tail gas, coke-stove gas, coal bed gas or calcium carbide tail gas.This method there are active ingredient utilization rate is low, product can not expire
The shortcomings of sufficient subsequent technique requirement.
There is an urgent need for a kind of calcium carbide stove exhausts with low hydrogen-carbon ratio to produce LNG, can improve the utilization ratio of effective ingredient
System.
Utility model content
The utility model is intended to provide one kind by low H2The system of the calcium carbide stove exhaust production LNG of/CO, the system have electricity
The advantages that stone furnace exhaust gas utilization rate of active components is high, and product meets subsequent technique requirement.
In one embodiment, the utility model provides a kind of system by calcium carbide stove exhaust production liquefied natural gas,
The system include sequentially connected dust-extraction unit, gas holder, the first compressor, first cleaning system, the second compressor, heat exchanger,
Change furnace, fine de-sulfur system, methane synthesis reaction system, NHD decarbonizing towers, MDEA decarbonizing towers, dehydration device, natural gas liquefaction system
System, the entrance of the dust-extraction unit are connected with calcium carbide stove exhaust feed pipe.
Further, dust-extraction unit is bag filter.
Further, the first compressor is helical-lobe compressor.
Further, first cleaning system includes sequentially connected preliminary clearning tower, dearsenicator, deep purifying tower, wherein pre- net
Change the filler that tower contains absorption fluoride and hydrogen phosphide, dearsenicator contains the filler of absorption arsenic hydride, and deep purifying tower contains suction
The filler of attached hydrogen phosphide.
Further, the second compressor is reciprocating compressor.
Further, fine de-sulfur system includes sequentially connected heat exchanger, waste heat boiler and medium temperature zinc oxide bath.
Further, methane synthesis reaction system include thermosistor, guard bed, first stage reactor, second stage reactor, three sections
Reactor, waste heat boiler, gas-liquid separator, recycle compressor,
Wherein, purification coal gas feed pipe is sequentially connected thermosistor, guard bed, goes out guard bed and is divided into two branches later, the
One branch connects first stage reactor import, the second branch connection second stage reactor import, the outlet conduit of first stage reactor via
Converge after waste heat boiler with the second branch, second stage reactor import is reconnected, after second stage reactor outlet is via waste heat boiler
Three sections of Reactor inlets are connected, three sections of reactor outlets are via connecting gas-liquid separator, the gas of gas-liquid separator after waste heat boiler
Phase outlet conduit is divided into two-way, is sent to subsequent processing all the way, and another way returns to first stage reactor import via recycle compressor.
Further, dehydration device is isobaric variable temperature dehydrating tower.
Further, natural gas liquefaction system includes natural gas liquefaction, separation and refrigerant compression cycle.
Included the following steps using above system by the method for calcium carbide stove exhaust production LNG：
(A) calcium carbide stove exhaust is forced into 0.4~0.8MPa, preferably 0.5~0.7MPa, more preferably from about 0.55MPa,
It is sent into tail gas clean-up (B) to purify calcium carbide stove exhaust, phosphide, arsenide in tail gas is dropped into 1mg/Nm3Hereinafter, it is preferred that
0.8mg/Nm3Hereinafter, more preferable 0.5mg/Nm3Hereinafter, total sulfur drops to 20ppm hereinafter, it is preferred that 18ppm is hereinafter, more preferable 15ppm
Below；
(C) purified tail gas is further forced into 2.0~3.0MPa, preferably 2.4~2.6MPa, more preferably from about
2.5MPa；
(D) by calcium carbide stove exhaust and water vapour by a certain percentage (such as 1：0.5~2 volume ratio, preferably 1:1.0~1.5
Volume ratio) it is mixed into change furnace, equipped with sulfur-resistant transformation catalyst (such as iron-chrome catalysts, cobalt-molybdenum catalysis in change furnace
Agent), transformation inlet temperature control is at 260-300 DEG C, preferably 270-290 DEG C, more preferably from about 280 DEG C, in this water and tail gas
Transformationreation occurs for CO, and the control of conversion gas outlet temperature is less than 450 DEG C, preferably shorter than 440 DEG C, more preferably less than 420 DEG C；
(E) methanation reaction, the appropriate conversion gas of hydrogen-carbon ratio that above-mentioned steps (D) obtain is in three sections of methanators
Methane synthetic reaction is carried out respectively, obtains synthesis gas, synthesis gas main ingredient is：CH4、CO2、N2、H2O；
(F) gas decarbonization is synthesized, by the CO in synthesis gas2Removing, the high methane gas after decarburization enter liquefying plant；With
(G) high methane gas liquefaction separation makees refrigerant using mix refrigerant, and methane liquefaction is obtained LNG, separation tail gas row
Enter air.
The key reaction formula of transformation is：CO+H2O→CO2+H2ΔH0=-41.9kJ/mol
Methane synthesis key reaction formula be：CO+3H2→CH4+H2OΔH0=-206.2kJ/mol
The molar ratio of methanation normal reaction hydrogen and carbon monoxide should be 3 it can be seen from methane synthetic reaction formula.Electricity
Stone furnace exhaust gas richness CO lacks H2, therefore, think to obtain methane as much as possible, require workshop section in front by transformationreation by H2/
CO be adjusted to 3 or so or more than 3 after enter back into methanation workshop section.
The 1mol CO and 1mol H it can be seen from transformationreation formula2Transformationreation, generation 1mol CO occur for O2With 1mol
H2, i.e. calcium carbide stove exhaust is after transformationreation, H in conversion gas2While content increase, CO2Content can also increase.
Methanation reaction is the reaction of volume-diminished it can be seen from methane synthetic reaction formula, therefore conversion gas passes through first
After alkylation reaction, CO in obtained synthesis gas2Content can become much larger.
Contain a large amount of CO2Synthesis gas enter ice chest before must first remove CO2It is, no that it will cause Cold box blocking and freezings.CO2It is de-
Except having dry removal technique and wet method removing process.CO2 contents are up to 70% in existing synthesis gas, ice chest import CO2Content will
It asks in below 1ppm.
High methane gas after decarburization carries out liquefaction separation processing, so as to obtain product LNG.
In addition, calcium carbide stove exhaust will be pressurizeed before being converted, purified treatment, to meet subsequent technique requirement.
In a preferred embodiment, it synthesizes in gas decarbonization, the CO of removing2It is discharged into air or for producing chemical fertilizer, vinegar
Acid etc..
In a preferred embodiment, the calcium carbide stove exhaust is using dry cleaning or wet cleaning or dry method wet method phase
With reference to purification method, calcium carbide stove exhaust impurity is made to reach subsequent technique requirement.
In a preferred embodiment, the synthesis gas decarbonization finds one kind most using dry method decarburization or wet method decarburization
Good decarburization mode, losing synthesis gas decarbonization effective ingredient, small, operating cost is low, one-time investment is small.
By the method for the utility model, can LNG be produced with the calcium carbide stove exhaust of low hydrogen-carbon ratio, can improved effectively
The utilization ratio of composition, while a kind of rational, system process is found, reduce equipment investment and operating cost.
Description of the drawings
Fig. 1 is the schematic diagram according to the system that LNG is produced by calcium carbide stove exhaust of the utility model.
Fig. 2 is the schematic diagram of the methane synthesis reaction system of the utility model, wherein, 1：Thermosistor；2：Guard bed；R1：
First stage reactor；R2：Second stage reactor；R3：Three sections of reactors；E1：Level-one waste heat boiler；E2：Two level waste heat boiler； E3：Three
Grade waste heat boiler；C1：Recycle compressor；V1：Gas-liquid separator.
Specific embodiment
The utility model is illustrated by specific embodiment below in conjunction with attached drawing.
As shown in Figure 1, the utility model provides a kind of system by calcium carbide stove exhaust production liquefied natural gas, the system packet
Include sequentially connected dust-extraction unit, gas holder, the first compressor, first cleaning system, the second compressor, heat exchanger, change furnace, essence
Desulphurization system, methane synthesis reaction system, NHD decarbonizing towers, MDEA decarbonizing towers, dehydration device, natural gas liquefaction system, it is described to remove
The entrance of dirt device is connected with calcium carbide stove exhaust feed pipe.
Dust-extraction unit can use bag filter.
Helical-lobe compressor may be used in first compressor.
First cleaning system may include sequentially connected preliminary clearning tower, dearsenicator, deep purifying tower, and wherein preliminary clearning tower contains
The filler of fluoride and hydrogen phosphide is adsorbed, dearsenicator contains the filler of absorption arsenic hydride, and deep purifying tower contains absorption hydrogen phosphide
Filler.
Second compressor can use reciprocating compressor.
Fine de-sulfur system may include sequentially connected heat exchanger, waste heat boiler and medium temperature zinc oxide bath.
Methane synthesis reaction system may include thermosistor, guard bed, first stage reactor, second stage reactor, three sections of reactors,
Waste heat boiler, gas-liquid separator, recycle compressor,
Wherein, purification coal gas feed pipe is sequentially connected thermosistor, guard bed, goes out guard bed and is divided into two branches later, the
One branch connects first stage reactor import, the second branch connection second stage reactor import, the outlet conduit of first stage reactor via
Converge after waste heat boiler with the second branch, second stage reactor import is reconnected, after second stage reactor outlet is via waste heat boiler
Three sections of Reactor inlets are connected, three sections of reactor outlets are via connecting gas-liquid separator, the gas of gas-liquid separator after waste heat boiler
Phase outlet conduit is divided into two-way, is sent to subsequent processing all the way, and another way returns to first stage reactor import via recycle compressor.
Isobaric variable temperature dehydrating tower may be used in dehydration device.
Natural gas liquefaction system may include natural gas liquefaction, separation and refrigerant compression cycle.
As shown in Fig. 2, methane synthesis reaction system may include thermosistor 1, guard bed 2, first stage reactor R1, second-stage reaction
Device R2, three sections of reactor R3, waste heat boiler E1, E2, E3, gas-liquid separator V1, recycle compressor C1,
Wherein, purification coal gas feed pipe is sequentially connected thermosistor 1, guard bed 2, goes out guard bed and is divided into two branches later,
The first branch connects first stage reactor R1 imports, the second branch connection second stage reactor R2 imports, the outlet of first stage reactor R1
Pipeline converges via after level-one waste heat boiler E1 with the second branch, reconnects second stage reactor R2 imports, second stage reactor R2
Outlet is via three sections of reactor R3 imports are connected after two level waste heat boiler E2, three sections of reactor R3 outlets are via three-level waste heat boiler
Gas-liquid separator V1 is connected after E3, the gaseous phase outlet pipeline of gas-liquid separator V1 is divided into two-way, is sent to subsequent processing all the way, another
Road returns to first stage reactor R1 imports via recycle compressor C1.
The method by calcium carbide stove exhaust production LNG of the utility model includes：Calcium carbide stove exhaust pressurization, purification, transformation, first
Alkane synthesis, CO2Removing, cryogenic liquefying process.
The calcium carbide stove exhaust will pass through bag filter before compressor is entered, and the dustiness in tail gas is dropped to
10mg/m3Below.
Calcium carbide stove exhaust after the dedusting is pressurized to 0.4~0.8MPa by helical-lobe compressor, preferably 0.5~
0.7MPa, more preferably from about 0.55MPa, into first purification.
The just purification uses physical absorption process, is respectively provided with to adsorb fluoride, hydrogen phosphide, arsenic in tower
The adsorbent (molecular sieve or modified molecules sieve adsorbant etc.) of the impurity such as hydrogen selectively removes the impurity in tail gas, excellent
Choosing makes hydrogen phosphide, hydrogen fluoride in tail gas etc. drop to 0.1ppm hereinafter, arsenic hydride drops to below 5ppb.
The just purified calcium carbide stove exhaust is forced into 2.0~3.0MPa through reciprocating compressor, preferably 2.4~
2.6MPa, more preferably from about 2.5MPa, into change furnace.
The calcium carbide stove exhaust of the 2.5MPa and water vapour by a certain percentage (such as 1：0.5~2 volume ratio, preferably 1:1.0
~1.5 volume ratio) change furnace is mixed into, exist in change furnace equipped with sulfur-resistant transformation catalyst, transformation inlet temperature control
200-260 DEG C, transformationreation occurs for the CO in this water and tail gas, controls interconversion rate, makes conversion gas H2/ CO=3, conversion gas go out
Mouth temperature control is less than 450 DEG C.
Transformationreation：CO+H2O→CO2+H2ΔH0=-41.9kJ/mol
Conversion gas after the transformation enters fine de-sulfur tower, and the total sulfur content in conversion gas is dropped to below 0.1ppm；Become
Ventilation main ingredient be：CH41.81%th, H241.06%th, CO 12.32%, CO241.25%th, N22.42%th, H2O
1.14%.
The suitable conversion gas of hydrogen-carbon ratio sent that converts carries out methane synthesis respectively in three sections of methanators
Reaction, obtains synthesis gas.
Methanation reaction：CO+3H2→CH4+H2OΔH0=-206.2kJ/mol
Contain about 70% CO in the synthesis gas2, using NHD decarbonization process, by CO2It takes off to less than 1.5%.
Through above-mentioned decarbonation process, CO2The synthesis gas of content ＜ 1.5%, using MDEA decarbonization process, by CO2It takes off to 30ppm
Hereinafter, referred to as high methane gas.
High methane gas enters dehydration device and carries out deep dehydration, and water content in gas is made to be down to below 1ppm.
Dewatered high methane gas enters ice chest, provides cold by mix refrigerant, makes CH4Liquefaction, with H2、N2Separation, obtains
To LNG；Separation tail gas is discharged into air.
The utility model feature is calcium carbide stove exhaust deep purifying, high CO2The gas of content takes off 30ppm, furnace of calcium carbide tail
The method that gas produces LNG.
The utility model is further described in detail with reference to the accompanying drawings of the specification, below only the utility model
Preferable example, it is impossible to which the scope of the utility model is limited with this.The change that every the scope of the claims of utility model application according to this is made
Change and modification, should all belong in the range of the utility model patent covers.
Embodiment
Process flow diagram as shown in Figure 1.
Treating capacity is the calcium carbide stove exhaust of 1000kmol/h, and pressure 0.01MPa, room temperature, gas molar composition is CO
85%, H24%, CO23.7%, CH43%, N24%, O20.3%；Gas dust content 150mg/m3, PH3 0.05%, HF
0.05%, H2S 0.2%, AsH3 0.01%.
Gas dust content through bag filter dedusting, is dropped to 10mg/m by tail gas first3Hereinafter, dry dedusting technology is simple
Single, ripe, wet dedusting complex process can generate sewage.
Tail gas after dedusting enters helical-lobe compressor and is pressurized to 0.55MPa into first cleaning procedure.
First cleaning system includes preliminary clearning tower, dearsenicator, deep purifying tower, and three towers are built-in to be useful for absorption fluoride, phosphorus
Change the adsorbent of the impurity such as hydrogen, arsenic hydride, preliminary clearning tower removes fluoride and most of hydrogen phosphide in gas, dearsenicator removing
Arsenic hydride in gas, deep purifying tower further remove hydrogen phosphide, PH in first purge outlet gas3≤ 0.1ppm, HF≤
0.1ppm, AsH3≤5ppb。
First purified tail gas is forced into 2.5MPa through reciprocating compressor and enters shift conversion step.
The tail gas for being pressurized to 2.5MPa exchanges heat through heat exchanger to about 300 DEG C, and 1 is pressed with water vapour:1 volume ratio mixing
About 280 DEG C of temperature enters change furnace afterwards, goes out change furnace CO about 13.2%, H2About 40.6%, about 450 DEG C of temperature, into heat exchanger
Heat exchange produces steam subsequently into waste heat boiler, and the conversion gas for pot outlet of giving up is through medium temperature zinc oxide bath, by the inorganic sulfur in gas
0.1ppm is removed to hereinafter, then sending synthesizing section.
Conversion gas into synthesizing section first passes around thermosistor adjusting temperature to about 200 DEG C, further into guard bed
The total sulfur in gas is made to be down to 0.02ppm, guard bed exit gas is divided to two strands to respectively enter one section of reaction after being preheating to about 280 DEG C
Device and second stage reactor, first gang of gas 400kmol/h enter after being mixed with the circulating air of three sections of reactor outlet about 650kmol/h
First stage reactor, second gang of gas 600kmol/h are mixed with gas of the first stage reactor exit gas after waste heat boiler recycles heat
It closes and enters second stage reactor, second stage reactor exit gas enters three sections of reactors, three sections of reactions through waste heat boiler recycling heat
First stage reactor entrance is partly recycled back to after the heat exchange of device exit gas, cooling, is partly sent to decarbonizing section, synthesis gas main ingredient
For：CH426.1%th, H20.35%th, CO269.48%th, N24.07%, tolerance about 980kmol/h.
High CO2The synthesis gas of content enters decarburization tower bottom, the solution counter current contacting sprayed with top, in gas
CO2It is absorbed by solution, decarbonization gas is sent out by tower top, and gas-liquid separation, gas-liquid separator exit gas are carried out into gas-liquid separator
For high methane gas, it is sent to dehydration procedure.NHD (polyethylene glycol dimethyl ether) decarbonizing towers are by the CO in gas2Take off to 1.5% hereinafter,
MDEA (N methyldiethanol amine) decarbonizing towers are by CO in gas2Take off below 30ppm.High methane gas main ingredient is：CH4
84.63%th, H21.17%th, N213.19%th, CO224ppm, tolerance about 288kmol/h.Absorbing liquid is through flash tank, regenerator
Posterior circle uses, the emptying of regeneration overhead gas, and main ingredient of dropping a hint is：CH41.82%th, CO296.73%th, N20.28%th,
H2O 1.17%, tolerance about 700kmol/h.NHD decarbonizing towers are two, and serial operation, First tower is void tower, bis- Tai Tanei
Fill regular packed tower.MDEA decarbonizing towers are one, built-in dumped packing.
High methane gas after decarburization enters isobaric variable temperature dehydrating tower, removes saturated water in gas.The built-in molecular sieve of dehydrating tower,
Complete an absorption, release, heating, cold blowing, release cyclic process within 8 hours.
Dewatered high methane gas enters natural gas liquefaction system, this system includes：Natural gas liquefaction, separation, refrigerant
Compression cycle.Obtain the LNG of purity >=99%, yield about 243kmol/h.Tail gas emptying is detached, main ingredient is：CH4
5.82%th, H28.03%th, N286.13%, tolerance about 42kmol/h.Technology involved by high methane gas cryogenic liquefying is in ability
Domain is known.
The utility model is described in detail above, but the utility model be not limited to it is described herein specific
Embodiment.It will be appreciated by those skilled in the art that in the case of without departing substantially from the scope of the utility model, can make other changes and
Deformation.The scope of the utility model is defined by the following claims.
Claims (9)
1. a kind of system by calcium carbide stove exhaust production liquefied natural gas, which is characterized in that the system includes sequentially connected remove
Dirt device, gas holder, the first compressor, first cleaning system, the second compressor, heat exchanger, change furnace, fine de-sulfur system, methane
Synthesis reaction system, NHD decarbonizing towers, MDEA decarbonizing towers, dehydration device, natural gas liquefaction system, the entrance of the dust-extraction unit
It is connected with calcium carbide stove exhaust feed pipe.
2. system according to claim 1, which is characterized in that dust-extraction unit is bag filter.
3. system according to claim 1, which is characterized in that the first compressor is helical-lobe compressor.
4. system according to claim 1, which is characterized in that first cleaning system includes sequentially connected preliminary clearning tower, takes off
Arsenic tower, deep purifying tower, wherein preliminary clearning tower contain the filler of absorption fluoride and hydrogen phosphide, and dearsenicator contains absorption arsenic hydride
Filler, deep purifying tower contain absorption hydrogen phosphide filler.
5. system according to claim 1, which is characterized in that the second compressor is reciprocating compressor.
6. system according to claim 1, which is characterized in that fine de-sulfur system includes sequentially connected heat exchanger, waste heat
Boiler and medium temperature zinc oxide bath.
7. according to the system described in any one of claim 1-6, which is characterized in that methane synthesis reaction system includes temperature adjustment
Device, guard bed, first stage reactor, second stage reactor, three sections of reactors, waste heat boiler, gas-liquid separator, recycle compressors,
Wherein, purification coal gas feed pipe is sequentially connected thermosistor, guard bed, goes out after guard bed and is divided into two branches, first
Road connects first stage reactor import, and the second branch connection second stage reactor import, the outlet conduit of first stage reactor is via waste heat
Converge with the second branch after boiler, reconnect second stage reactor import, second stage reactor outlet after waste heat boiler via connecting
Three sections of Reactor inlets, three sections of reactor outlets go out via gas-liquid separator, the gas phase of gas-liquid separator is connected after waste heat boiler
Mouth pipeline is divided into two-way, is sent to subsequent processing all the way, and another way returns to first stage reactor import via recycle compressor.
8. system according to claim 1, which is characterized in that dehydration device is isobaric variable temperature dehydrating tower.
9. system according to claim 1, which is characterized in that natural gas liquefaction system include natural gas liquefaction, separation and
Refrigerant compression cycle.
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