CN104150441B - A kind of Fischer-Tropsch process exhaust is converted into the method for F-T synthesis unstripped gas - Google Patents
A kind of Fischer-Tropsch process exhaust is converted into the method for F-T synthesis unstripped gas Download PDFInfo
- Publication number
- CN104150441B CN104150441B CN201410366341.0A CN201410366341A CN104150441B CN 104150441 B CN104150441 B CN 104150441B CN 201410366341 A CN201410366341 A CN 201410366341A CN 104150441 B CN104150441 B CN 104150441B
- Authority
- CN
- China
- Prior art keywords
- gas
- fischer
- tropsch process
- process exhaust
- converted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method that Fischer-Tropsch process exhaust is converted into F-T synthesis unstripped gas is that Fischer-Tropsch process exhaust passes through in the hydrogenator that hydrogenation catalyst is housed, carry out catalytic hydrogenation reaction and is converted into stable hydrocarbon, steam reforming and partial oxidation is carried out again at one-stage converter and secondary reformer, water gas shift reation is carried out in middle change stove, finally carry out gas-liquid separation, gas phase is for meeting the unstripped gas of the hydrogen carbon proportioning required by F-T synthesis.The present invention has simple, the easy to operate advantage of technique.
Description
Technical field
The present invention relates to a kind of method Fischer-Tropsch process exhaust being converted into F-T synthesis unstripped gas.
Background technology
Fischer-Tropsch process exhaust refers to through synthetic gas (H
2with CO) be converted into through Fischer-Tropsch synthesis in the presence of a catalyst produce in the process of hydrocarbon compound primarily of H
2, CO, CO
2and the mixed gas of the composition such as lower carbon number hydrocarbons.Wherein, lower carbon number hydrocarbons is with CH
4be main, its content, usually at 20-60% (molar percentage), also contains the low-carbon alkene of 1-10% (molar percentage) in addition in lower carbon number hydrocarbons.At present in disclosed prior art, the utilization of Fischer-Tropsch process exhaust mainly contains two kinds of modes, and one can obtain H by being separated
2with methane combustion gas etc.; Another kind is that hydrocarbon compound in tail gas (mainly methane) is converted into synthetic gas, then returns the further synthetic oil of F-T synthesis unit as unstripped gas, thus improves raw material availability and oil product yield.
Patent CN101273112B discloses a kind of method with transformation of synthetic gas of preparing, and the method is to containing CH in conversion stages
4unstripped gas carry out converting to generate H
2with CO synthetic gas, and then for Fischer-Tropsch synthesis, the tail gas of F-T synthesis is then by the CH in steam shift tail gas
4, and remove CO
2thus generation hydrogen-rich gas.
Patent CN102614763A discloses a kind for the treatment of process of Fischer-Tropsch process exhaust, and comprise decarburization, membrane sepn, low temperature oil wash, tail gas conversion and pressure-variable adsorption step, this treatment process need remove the CO in Fischer-Tropsch process exhaust through decarburization
2component, and then reclaim H through film separation unit and crude synthesis gas through conversion and psa unit
2for full factory, resolution gas is then made fuel gas and is used.
Patent CN102614764B discloses a kind of technique of Fischer-Tropsch process exhaust preparing high purity hydrogen, and this technique comprises lighter hydrocarbons partial oxidation, conversion, decarburization, pressure-variable adsorption four steps, can obtain the hydrogen that purity reaches more than 99%.Therefore, the main purpose of this technique is preparing high purity hydrogen.
Patent CN102703108A provides the processing method of a kind of F-T synthesis and waste gas utilization, the method utilizes pressure swing adsorption from Fischer-Tropsch process exhaust, extract hydrogen and methane, then mix with F-T synthesis unstripped gas according to a certain percentage, thus realize the recycle of Fischer-Tropsch process exhaust.The main purpose of the method reduces the load of shift conversion step in F-T synthesis device, thus improve production efficiency and the economy of F-T synthesis device, but to H in the method
2and CH
4control of purity require higher.
Patent CN102730637A discloses a kind of Fischer-Tropsch process exhaust comprehensive utilization process of low-carbon emission, and the not recycled offgas after Fischer-Tropsch synthesis is converted into hydrogen-rich gas by this technique, and from hydrogen-rich gas, extract the process that high-purity hydrogen is used.
Containing CO in Fischer-Tropsch process exhaust
2, part lower carbon number hydrocarbons, and the hydrogen-carbon ratio in tail gas directly cannot meet the requirement of F-T synthesis, Fischer-Tropsch process exhaust is converted into F-T synthesis unstripped gas, thus can improve the utilization ratio of carbon and the throughput of synthetic oil device, does not find report through retrieval.
Summary of the invention
The object of this invention is to provide the method that simple, the easy to operate Fischer-Tropsch process exhaust of a kind of technique is converted into F-T synthesis unstripped gas.
The present invention is by carrying out shortening, steam reformation, partial oxidation and water-gas shift process adjustments to lower carbon number hydrocarbons unsaturated in Fischer-Tropsch process exhaust, obtains and is suitable for as the H required by F-T synthesis gas
2the unstripped gas of/CO proportioning.
The technical solution adopted in the present invention is:
A kind of method Fischer-Tropsch process exhaust being converted into F-T synthesis unstripped gas, comprise shortening, steam reformation and partial oxidation reaction, middle temperature water gas shift reation, waste heat recovery and gas-liquid separation four operations, it is characterized in that described shortening operation is by carrying out catalytic hydrogenation reaction in the hydrogenator that hydrogenation catalyst is housed, hydrogenation of unsaturated hydrocarbons in Fischer-Tropsch process exhaust is converted into stable hydrocarbon; described steam reforming and partial oxidation reaction operation comprise one-stage converter and secondary reformer two converters, the mixed gas that water vapour and the described Fischer-Tropsch process exhaust through shortening form enters the one-stage converter that reforming catalyst A is housed and completes primary transformants, enter from one-stage converter gas out in the secondary reformer that reforming catalyst B is housed, pass in secondary reformer through the pure oxygen of preheating simultaneously and carry out a small amount of Fischer-Tropsch process exhaust oxidizing reaction and complete deep conversion, by controlling the intake of steam and pure oxygen, to the carbon ratio of mixed gas in the steam/hydrocarbons ratio of mixed gas in one-stage converter and secondary reformer, and the service temperature of one-stage converter and secondary reformer and working pressure regulate, finally carry out water gas shift reation being equipped with in catalyzer to become in stove, described waste heat recovery and gas-liquid separation operation are that material water gas shift reation obtained is first through reclaiming heat, carry out gas-liquid separation again, gas phase is for meeting the unstripped gas of the hydrogen carbon proportioning required by F-T synthesis.
Further, described one-stage converter is outside equipped with double-pipe exchanger, partial heat is delivered to double-pipe exchanger by the high temperature two process transform gas coming from described secondary reformer, then carry out heat exchange by between the reactant in double-pipe exchanger and one-stage converter, thus provide thermal source for the reforming reaction in one-stage converter; Heat needed for transforming in described secondary reformer is by passing into pure oxygen in secondary reformer, is provided by hydrogen, methane, carbon monoxide and pure oxygen generation combustion reactions in part one section of reforming gas of secondary reformer furnace roof.
Further, in described shortening operation, hydrogenation catalyst is JT-202, and service temperature is 220-250 DEG C, and working pressure is 2.0-3.0MPa, and air speed is 1000-2000h
-1.
Further, the reforming catalyst A used in described one-stage converter is Z112-HA and Z112-HB, in one-stage converter, the water carbon mol ratio of mixed gas is 2.5-3.5 (stream molecule number): 1 (carbonatoms), service temperature is 650-850 DEG C, working pressure is 2.0-3.0MPa, and air speed is 1000-2000h
-1.
The change of described steam vapour amount and control utilize this index of steam/hydrocarbons ratio to calculate and weigh, and its definition is one section of ratio being transformed into the stream molecule number in furnace gas and the carbonatoms of raw material hydrocarbon.Steam/hydrocarbons ratio is implication index more accurately, when calculating proportioning raw materials, first requires the total carbon atom number (usually writing ∑ C) calculated contained by per molecule gas, then compared with water vapour molecule number.
∑C＝1×C1+2×C2+3×C3+……+n×Cn(1)
Wherein C1, C2, C3, Cn be respectively carbon atom quantity in unstripped gas be 1,2,3, n is the volume fraction of hydro carbons.Such as, not only containing methane in described raw material Fischer-Tropsch process exhaust, a small amount of ethane is also had.When with steam reaction, a part methane calculates by a carbon atom, and a part ethane calculates by two carbonatomss, and the carbonatoms of other hydro carbons by that analogy.
Further, described water vapour is temperature is 200-300 DEG C, pressure is the saturated vapor of 2.0-3.0MPa.
Further, the weight ratio of described Z112-HA and Z112-HB is (0.8-1.2): (0.8-1.2).
Further, the described oxygen through preheating enters secondary reformer, is 0.4-0.6 with the oxygen carbon mol ratio of two process transform furnace gas.
The change of described partial oxidation reaction and control utilize carbon ratio index to calculate and weigh, its definition passes into the molar weight of oxygen and the ratio of alkane carbon atom mole number in two process transform gas in secondary reformer, in this definition the statistical method of carbon atom mole number define with above-mentioned steam/hydrocarbons ratio in the statistical method of carbon atom mole number identical.
Further, the reforming catalyst B in described secondary reformer is CZ-7, and service temperature is 850-1300 DEG C, and working pressure is 2.0-3.0MPa, and air speed is 1000-2000h
-1.
Further, the catalyzer in described middle change stove is NB113, and service temperature is 340-360 DEG C, and working pressure is 2.0-3.0MPa, and air speed is 1000-2000h
-1.
Further, H in the F-T synthesis unstripped gas obtained according to method of the present invention
2the ratio of/CO is 2.9-3.5.
The present invention compared with prior art has following remarkable advantage:
The method of the invention is by controlling the intake of steam and pure oxygen, the operation such as steam/hydrocarbons ratio and carbon ratio in steam reformation and partial oxidation reaction process is regulated, the unstripped gas be suitable for as the hydrogen-carbon ratio proportioning required by F-T synthesis can be obtained, F-T synthesis raw material is obtained utilize more fully, carbon utilisation rate is improved, technique is simple, easy to operate, thus overcome in prior art by Fischer-Tropsch process exhaust treatment process by hydrogen and methane respectively separation and Extraction out, then carry out the technical sophistication that utilizes and the high technical problem of difficulty.
Accompanying drawing explanation
Fig. 1 is technological process of production schematic diagram of the present invention.
In figure, 1 is interchanger; 2 is hydrogenators; 3 is heating muffs; 4 is one-stage converters; 5 is secondary reformers; 6 is interchanger; 7 is middle change stoves; 8 is waste heat boilers; 9 is gas-liquid separators.
Embodiment
Below in conjunction with object of the present invention, principle, technical scheme of the present invention is described in detail.
The present invention take Fischer-Tropsch process exhaust as raw material, F-T synthesis unstripped gas is translated into by steam reforming process, technical essential of the present invention hydro carbons unsaturated in Fischer-Tropsch process exhaust is carried out to the adjustment of the techniques such as hydrogenation reaction, steam reformation, partial oxidation, thus reach obtain be suitable for as the H required by F-T synthesis gas
2the unstripped gas of/CO proportioning.
In the inventive method, the change of described steam vapour amount and control utilize this index of steam/hydrocarbons ratio to calculate and weigh, and its definition is one section of ratio being transformed into the stream molecule number in furnace gas and the carbonatoms of raw material hydrocarbon.Steam/hydrocarbons ratio is implication index more accurately, when calculating proportioning raw materials, first requires the total carbon atom number (usually writing ∑ C) calculated contained by per molecule gas, then compared with water vapour molecule number.
∑C＝1×C1+2×C2+3×C3+……+n×Cn(1)
Wherein C1, C2, C3, Cn be respectively carbon atom quantity in unstripped gas be 1,2,3, n is the volume fraction of hydro carbons.Such as, not only containing methane in described raw material Fischer-Tropsch process exhaust, a small amount of ethane is also had.When with steam reaction, a part methane calculates by a carbon atom, and a part ethane calculates by two carbonatomss, and the carbonatoms of other hydro carbons by that analogy.
In the inventive method, the change of described partial oxidation reaction and control utilize carbon ratio index to calculate and weigh, its definition passes into the amount of oxygen and the ratio of alkane carbon atom mole number in two process transform gas in secondary reformer, in this definition the statistical method of carbon atom mole number define with above-mentioned steam/hydrocarbons ratio in the statistical method of carbon atom mole number identical.
Under the guidance of above-mentioned purpose and principle, the present invention proposes following Fischer-Tropsch process exhaust conversion process:
A kind of method Fischer-Tropsch process exhaust being converted into F-T synthesis unstripped gas of the present invention comprises shortening, steam reformation and partial oxidation reaction, middle temperature water gas shift reation, waste heat recovery and gas-liquid separation four operations.
(1) shortening operation
Very easily in follow-up conversion process, there is carbon deposition phenomenon in the unsaturated hydrocarbons in Fischer-Tropsch process exhaust, affect subsequent transformation operation, especially the normal operation of one-stage converter, therefore the main purpose of this operation is, by carrying out catalytic hydrogenation reaction in hydrogenator 2, hydrogenation of unsaturated hydrocarbons in Fischer-Tropsch process exhaust is converted into stable hydrocarbon, and concrete reaction is as follows:
This operation adopts the hydrogenation conversion catalyst JT-202 not needing special activation treatment, and described hydrogenation conversion catalyst is purchased from Xibei Chemical Inst.The model of this hydrogenation conversion catalyst, composition, character and consumption situation refer to table 1.
Table 1
The stable hydrocarbon (C2 ~ C4) generated after this operation hydrogenation reaction also can increase the possibility generating carbon deposit, regulates the consumption of water vapour to be controlled by follow-up steam reforming reaction and partial oxidation reaction operation.
As shown in Figure 1, Fischer-Tropsch process exhaust enters hydrogenator 2 after interchanger 1 preheating, under the effect of catalyzer, carry out hydrogenation reaction, and after hydrogenation reaction, mixed gas enters one-stage converter 4 and carries out reforming reaction.
(2) steam reforming and partial oxidation reaction
This operation comprises one-stage converter 4 and secondary reformer 5, and main purpose is by carrying out steam reformation in one-stage converter 4 and secondary reformer 5 and partial oxidation reaction generates H to greatest extent
2and CO.
This operation one-stage converter 4 and secondary reformer 5 use the model of catalyzer, composition, character and consumption situation to refer to table 2.
Table 2
As shown in Figure 1, the mixed gas of the Fischer-Tropsch process exhaust after the saturated vapor that temperature is 200-300 DEG C, pressure is 2.0-3.0MPa and hydrogenation enters in one-stage converter 4, Z112-HA, Z112-HB catalyzer simultaneously in the presence of, carry out the steam reformation conversion reaction of gaseous alkanes.Described one-stage converter 4 one section of reforming gas out enters in secondary reformer 5, by the pure oxygen through preheating by the carbon ratio described in the embodiment of the present invention, passes in secondary reformer 5 meanwhile.Described one section of transformation of synthetic gas and described pure oxygen mix in described secondary reformer 5, and H occurs
2and small part CH
4, CO and O
2combustion reactions.Remaining gas, in secondary reformer 5, carries out deep conversion under the pressure and CZ-7 type catalyzer existent condition of 2.0-3.0MPa, CH remaining in two process transform gas
4content is down to 0.5% (butt, volume percent) below.
In this operation steam reforming reaction and water gas shift reation equation as follows:
CH
4+H
2O＝CO+3H
2-ΔQ
1(3)
C
nH
2n+2+nH
2O＝nCO+(2n+1)H
2-ΔQ
2(4)
CO+H
2O＝CO
2+H
2+ΔQ
3(5)
The equilibrium composition composition of described one-stage converter 4 depends on reaction (3) and (5).This is because steam/hydrocarbons ratio improves, namely water vapor increases the carrying out being conducive to methane reforming reaction.But not remarkable to the effect of increase methane conversion after steam/hydrocarbons ratio to certain value, and excessive steam/hydrocarbons ratio easily causes the Pressure Drop in converter to increase, and then increase the consumption of water vapor.Steam/hydrocarbons ratio reduces and then easily causes catalyst carbon deposition, thus strictly should control steam/hydrocarbons ratio.In described steam reformation conversion process, in one-stage converter, the control of steam/hydrocarbons ratio and adjustment are one of key problem in technology of the present invention.In the inventive method, the service temperature in described one-stage converter 4 is 650-850 DEG C, and working pressure is 2.0-3.0MPa, and the steam/hydrocarbons ratio of mixed gas is 2.5-3.5.
In above-mentioned steam reformation conversion process, the heat needed for described one section of reforming reaction process is from reacting the heat discharged in secondary reformer 5.Described one-stage converter 4 is outside equipped with double-pipe exchanger 3, and partial heat is delivered to described double-pipe exchanger 3 by the high temperature two process transform gas coming from secondary reformer 5, then transfers heat to described one-stage converter 4 through described double-pipe exchanger 3.The interior one section of reforming gas heat carried out further needed for hydrocarbon conversion reactions of described secondary reformer 5 is then by passing into pure oxygen in the combustion chamber of secondary reformer 5, then generating portion oxidizing reaction in this combustion chamber, is namely provided by the combustion reactions of hydrogen, portion of methane, carbon monoxide and oxygen.Concrete reaction equation is as follows:
CH
4+2O
2＝CO
2+2H
2O+ΔQ
5(7)
Because combustion of hydrogen speed of response is very fast, so the combustion reactions of the mainly hydrogen in fact carried out at this position.This position top temperature is between 1400-1600 DEG C.Therefore in secondary reformer, the control of carbon ratio and adjustment are another key problem in technology of the present invention.In the inventive method, the carbon ratio of the mixed gas in described secondary reformer 5 is 0.4-0.6, and oxygen described in this process needed to be heated to as 100-500 DEG C before passing in Fischer-Tropsch process exhaust.By controlling and regulate the carbon ratio of the mixed gas in secondary reformer 5, the service temperature in described secondary reformer 5 is controlled is made as 850-1300 DEG C, and working pressure is 2.0-3.0MPa.
On beds in secondary reformer 5, there is steam reforming reaction (3) and water gas shift reation (5) in residue methane further.The composition of two process transform gas depends on transformationreation (5).By to the above-mentioned control carried out in secondary reformer and adjustment, the content of methane is finally made to reduce to 0.5v% (butt, volume percent) below.
(3) stove water gas shift reation is become in
Gas after two process transform enters middle change stove after repeatedly recovery waste heat, and in middle change stove, water gas shift reation (5) occurs part CO, thus the hydrogen-carbon ratio of adjustable Fischer-Tropsch process exhaust.
Due to the thermopositive reaction that reaction is reversible, reduce temperature or increase excessive water vapor, be all conducive to transformationreation and carry out to the right, transformationreation can accelerate its speed of response greatly by means of catalyzer, by the Partial Transformation being actually CO carried out in this device, can by H
2/ CO ratio is adjusted to 2.9 ~ 3.5, thus meets the requirement of F-T synthesis.
Table 3
| Catalyzer model | Catalyzer forms | |
| Middle change stove 7 | NB113 | Fe 2O 3≥75％，Cr 2O 3≥7.5％ |
(4) waste heat recovery and gas-liquid separation
The main purpose of this operation is the material synthesis gas reclaiming heat to greatest extent and obtain the hydrogen-carbon ratio proportioning met required by F-T synthesis.
Two process transform gas after net quantity of heat reclaims finally cools and isolates free-water through gas-liquid separator 9, can obtain the unstripped gas of the hydrogen-carbon ratio proportioning met required by F-T synthesis.
Waste heat recovery process is actually carries out for carrying out combustion reactions institute liberated heat in secondary reformer 5.Through combustion reactions gained two process transform gas entrained by heat be delivered to described double-pipe exchanger 3, for the reforming reaction in one-stage converter 4 provides thermal source, after gas after double-tube heat exchanger 3 heat exchange enters interchanger 6, part heat is used for middle change stove 7 provides reaction heat, another part heat carries out heat recuperation through waste heat boiler 8, and enters interchanger 1 for preheating Fischer-Tropsch process exhaust.
Below in conjunction with accompanying drawing and most preferred embodiment, the present invention is described in further detail.
Embodiment 1
(1) 40 DEG C, 2.4MPa, air speed be 1500h
-1fischer-Tropsch process exhaust (its main component is 16.4%CO, 40.3%H
2, 40.2%CH
4, 1.2% lower carbon number hydrocarbons, 0.1%CO
2, 1.83%N
2) be preheated to 200 DEG C after enter hydrogenator 2, under the effect of catalyzer JT-202 in 230 DEG C, 2.4MPa, air speed be 1500h
-1hydrogenation reaction is carried out, C under condition
2h
4and C
3h
6all be converted into C
2h
6and C
3h
8, the gas after hydrogenation with 230 DEG C, the saturation steam of 2.4MPa by steam/hydrocarbons ratio be 3.0 mix after be warming up to 500 DEG C and enter in one-stage converter 4;
(2) enter mixed gas in one-stage converter 4 under catalyst Z 112-HA and Z112-HB exists by weight 1:1, service temperature is 720 DEG C, pressure 2.4MPa, air speed are 1500h
-1, and the heat source of partial heat as reaction of heat exchange type sleeve pipe 3 is supplied by the pyrolytic conversion air lift from secondary reformer 5, carry out the steam reformation conversion reaction of gaseous alkanes, work off one's feeling vent one's spleen middle CH
4content is down to 18.7%, then enters in secondary reformer 5, is 0.45 by carbon ratio, and by O
2mix in secondary reformer 5 with one section of reforming gas after being preheated to 200 DEG C, H occurs
2and part CH
4, CO and O
2combustion reactions, its reaction heat provides required heat for the reaction of methane deep conversion, remaining gas in secondary reformer 5, catalyzer CZ-7,1000 DEG C, 2.4MPa, air speed be 1500h
-1deep conversion is carried out, remaining CH in two process transform gas under condition
4content is down to 0.50v% (butt);
(3) partial heat is delivered to described double-pipe exchanger 3 for conversion reaction in one-stage converter 4 by two process transform gas provides thermal source, after the heat after double-tube heat exchanger 3 heat exchange passes into interchanger 6, part heat is used for middle change stove 7 provides reaction heat, another part heat carries out heat recuperation through waste heat boiler 8, and enters interchanger 1 for preheating Fischer-Tropsch process exhaust.
Two process transform gas after net quantity of heat reclaims is under the existence that is NB113 of middle change stove 7 inner catalyst, and service temperature is 360 DEG C, and working pressure is 2.4MPa, and air speed is 1000h
-1under carry out water gas shift reation, finally cool and isolate free-water through gas-liquid separator 9, the unstripped gas of the hydrogen-carbon ratio proportioning met required by F-T synthesis can be obtained.
Embodiment 2
(1) 40 DEG C, 2.5MPa, air speed be 1200h
-1fischer-Tropsch process exhaust (its main component is 16.4%CO, 40.3%H
2, 40.2%CH
4, 1.2% lower carbon number hydrocarbons, 0.1%CO
2, 1.83%N
2) be preheated to 220 DEG C after enter hydrogenator 2, under the effect of catalyzer JT-202 in 220 DEG C, 2.5MPa, air speed be 1100h
-1hydrogenation reaction is carried out, C under condition
2h
4and C
3h
6all be converted into C
2h
6and C
3h
8, the gas after hydrogenation with 230 DEG C, the saturation steam of 2.5MPa by steam/hydrocarbons ratio be 2.9 mix after be warming up to 500 DEG C and enter in one-stage converter 4;
(2) enter mixed gas in one-stage converter 4 under catalyst Z 112-HA and Z112-HB exists by weight 0.9:1.1, service temperature is 740 DEG C, pressure 2.5MPa, air speed are 1100h
-1, and the heat source of partial heat as reaction of heat exchange type sleeve pipe 3 is supplied by the pyrolytic conversion air lift from secondary reformer 5, carry out the steam reformation conversion reaction of gaseous alkanes, work off one's feeling vent one's spleen middle CH
4content is down to 19.5%, then enters in secondary reformer 5, is 0.5 by carbon ratio, and by O
2mix in secondary reformer 5 with one section of reforming gas after being preheated to 200 DEG C, H occurs
2and part CH
4, CO and O
2combustion reactions, its reaction heat provides required heat for the reaction of methane deep conversion, remaining gas in secondary reformer 5, catalyzer CZ-7,1100 DEG C, 2.5MPa, air speed be 1100h
-1deep conversion is carried out, remaining CH in two process transform gas under condition
4content is down to 0.49v% (butt);
(3) becoming stove 7 inner catalyst in is NB113, and service temperature is 350 DEG C, and working pressure is 2.5MPa, and air speed is 1200h
-1under carry out water gas shift reation, other conditions are with (3) in embodiment 1.
Embodiment 3
(1) 40 DEG C, 2.3MPa, air speed be 1000h
-1fischer-Tropsch process exhaust (its main component is 16.4%CO, 40.3%H
2, 40.2%CH
4, 1.2% lower carbon number hydrocarbons, 0.1%CO
2, 1.83%N
2) be preheated to 240 DEG C after enter hydrogenator 2, under the effect of catalyzer JT-202 in 230 DEG C, 2.3MPa, air speed be 1200h
-1hydrogenation reaction is carried out, C under condition
2h
4and C
3h
6all be converted into C
2h
6and C
3h
8, the gas after hydrogenation with 230 DEG C, the saturation steam of 2.3MPa by steam/hydrocarbons ratio be 2.7 mix after be warming up to 500 DEG C and enter in one-stage converter 4;
(2) mixed gas entered in one-stage converter 4 is that under 0.8:1 exists, service temperature is 800 DEG C, working pressure 2.3MPa, air speed are 1200h at catalyst Z 112-HA and Z112-HB weight ratio
-1, and the heat source of partial heat as reaction of heat exchange type sleeve pipe 3 is supplied by the pyrolytic conversion air lift from secondary reformer 5, carry out the steam reformation conversion reaction of gaseous alkanes, work off one's feeling vent one's spleen middle CH
4content is down to 20.5%, then enters in secondary reformer 5, is 0.6 by carbon ratio, and by O
2mix in secondary reformer 5 with one section of reforming gas after being preheated to 200 DEG C, H occurs
2and part CH
4, CO and O
2combustion reactions, its reaction heat provides required heat for the reaction of methane deep conversion, remaining gas in secondary reformer 5, catalyzer CZ-7,1300 DEG C, 2.3MPa, air speed be 1200h
-1deep conversion is carried out, remaining CH in two process transform gas under condition
4content is down to 0.5v% (butt);
(3) becoming stove 7 inner catalyst in is NB113, and service temperature is 360 DEG C, and working pressure is 2.3MPa, and air speed is 1200h
-1under carry out water gas shift reation, other conditions are with (3) in embodiment 1.
The concrete component molar composition of synthetic gas and H
2/ CO ratio is in table 4.
Embodiment 4
(1) 40 DEG C, 2.1MPa, air speed be 1800h
-1fischer-Tropsch process exhaust (its main component is 16.4%CO, 40.3%H
2, 40.2%CH
4, 1.2% lower carbon number hydrocarbons, 0.1%CO
2, 1.83%N
2) be preheated to 200 DEG C after enter hydrogenator 2, under the effect of catalyzer JT-202 in 240 DEG C, 2.1MPa, air speed be 1800h
-1hydrogenation reaction is carried out, C under condition
2h
4and C
3h
6all be converted into C
2h
6and C
3h
8, the gas after hydrogenation with 230 DEG C, the saturation steam of 2.1MPa by steam/hydrocarbons ratio be 3.0 mix after be warming up to 500 DEG C and enter in one-stage converter 4;
(2) mixed gas entered in one-stage converter 4 is that under 1.1:0.9 exists, service temperature is 720 DEG C, working pressure 2.1MPa, air speed are 1800h at catalyst Z 112-HA and Z112-HB weight ratio
-1, and the heat source of partial heat as reaction of heat exchange type sleeve pipe 3 is supplied by the pyrolytic conversion air lift from secondary reformer 5, carry out the steam reformation conversion reaction of gaseous alkanes, work off one's feeling vent one's spleen middle CH
4content is down to 17.9%, then enters in secondary reformer 5, is 0.42 by carbon ratio, and by O
2mix in secondary reformer 5 with one section of reforming gas after being preheated to 200 DEG C, H occurs
2and part CH
4, CO and O
2combustion reactions, its reaction heat provides required heat for the reaction of methane deep conversion, remaining gas in secondary reformer 5, catalyzer CZ-7,1000 DEG C, 2.1MPa, air speed be 1800h
-1deep conversion is carried out, remaining CH in two process transform gas under condition
4content is down to 0.45v% (butt);
(3) becoming stove 7 inner catalyst in is NB113, and service temperature is 360 DEG C, and working pressure is 2.1MPa, and air speed is 1800h
-1under carry out water gas shift reation, other conditions are with (3) in embodiment 1.
Embodiment 5
(1) 40 DEG C, 2.4MPa, air speed be 1200h
-1fischer-Tropsch process exhaust (its main component is 16.4%CO, 40.3%H
2, 40.2%CH
4, 1.2% lower carbon number hydrocarbons, 0.1%CO
2, 1.83%N
2) be preheated to 200 DEG C after enter hydrogenator 2, under the effect of catalyzer JT-202 in 230 DEG C, 2.4MPa, air speed be 1000h
-1hydrogenation reaction is carried out, C under condition
2h
4and C
3h
6all be converted into C
2h
6and C
3h
8, the gas after hydrogenation with 230 DEG C, the saturation steam of 2.4MPa by steam/hydrocarbons ratio be 3.1 mix after be warming up to 500 DEG C and enter in one-stage converter 4;
(2) enter mixed gas in one-stage converter 4 under catalyst Z 112-HA and Z112-HB exists by weight 1:1, service temperature is 710 DEG C, working pressure 2.4MPa, air speed are 1000h
-1, and the heat source of partial heat as reaction of heat exchange type sleeve pipe 3 is supplied by the pyrolytic conversion air lift from secondary reformer 5, carry out the steam reformation conversion reaction of gaseous alkanes, work off one's feeling vent one's spleen middle CH
4content is down to 16.2%, then enters in secondary reformer 5, is 0.48 by carbon ratio, and by O
2mix in secondary reformer 5 with one section of reforming gas after being preheated to 200 DEG C, H occurs
2and part CH
4, CO and O
2combustion reactions, its reaction heat provides required heat for the reaction of methane deep conversion, remaining gas in secondary reformer 5, catalyzer CZ-7,1050 DEG C, 2.4MPa, air speed be 1000h
-1deep conversion is carried out, remaining CH in two process transform gas under condition
4content is down to 0.48v% (butt);
(3) becoming stove 7 inner catalyst in is NB113, and service temperature is 360 DEG C, and working pressure is 2.4MPa, and air speed is 1000h
-1under carry out water gas shift reation, other conditions are with (3) in embodiment 1.
Embodiment 6
(1) 40 DEG C, 2.8MPa, air speed be 1200h
-1fischer-Tropsch process exhaust (its main component is 16.4%CO, 40.3%H
2, 40.2%CH
4, 1.2% lower carbon number hydrocarbons, 0.1%CO
2, 1.83%N
2) be preheated to 200 DEG C after enter hydrogenator 2, under the effect of catalyzer JT-202 in 230 DEG C, 2.8MPa, air speed be 1200h
-1hydrogenation reaction is carried out, C under condition
2h
4and C
3h
6all be converted into C
2h
6and C
3h
8, the gas after hydrogenation with 230 DEG C, the saturation steam of 2.8MPa by steam/hydrocarbons ratio be 3.3 mix after be warming up to 500 DEG C and enter in one-stage converter 4;
(2) enter mixed gas in one-stage converter 4 under catalyst Z 112-HA and Z112-HB exists by weight 1:0.9, service temperature is 680 DEG C, working pressure 2.8MPa, air speed are 1200h
-1, and the heat source of partial heat as reaction of heat exchange type sleeve pipe 3 is supplied by the pyrolytic conversion air lift from secondary reformer 5, carry out the steam reformation conversion reaction of gaseous alkanes, work off one's feeling vent one's spleen middle CH
4content is down to 19.5%, then enters in secondary reformer 5, is 0.5 by carbon ratio, and by O
2mix in secondary reformer 5 with one section of reforming gas after being preheated to 200 DEG C, H occurs
2and part CH
4, CO and O
2combustion reactions, its reaction heat provides required heat for the reaction of methane deep conversion, remaining gas in secondary reformer 5, catalyzer CZ-7,900 DEG C, 2.8MPa, air speed be 1200h
-1deep conversion is carried out, remaining CH in two process transform gas under condition
4content is down to 0.40v% (butt);
(3) becoming stove 7 inner catalyst in is NB113, and service temperature is 350 DEG C, and working pressure is 2.8MPa, and air speed is 1500h
-1under carry out water gas shift reation, other conditions are with (3) in embodiment 1.
In preferred embodiment 1 ~ 6, in the operational condition of shortening 2, one-stage converter 4 in the steam/hydrocarbons ratio of mixed gas and secondary reformer 5 carbon ratio of mixed gas, one-stage converter 4 and the operational condition of secondary reformer 5 and the operational condition of middle change stove etc. in table 4 and 5.The concrete component molar composition of the synthetic gas of final acquisition and H
2/ CO ratio is in table 6.
Table 4 shortening and one-stage converter operational condition
Table 5 secondary reformer and middle change furnace operating condition
The composition of table 6 product synthetic gas
In prior art with Fischer-Tropsch synthesis oil tail gas for raw material, obtain synthetic gas by steam reformation, to return in the technology gained synthetic gas that F-T synthesis device utilizes again H in steam reformation gas
2higher, CO content is lower, H
2/ CO reaches more than 4.22.From table 6, according to CH in the unstripped gas that method of the present invention obtains
4content below 0.5, H
2the ratio of/CO is 2.9 ~ 3.5.The synthetic gas that method of the present invention obtains directly is passed in the material synthesis gas of Fischer-Tropsch synthesis oil, thus Fischer-Tropsch process exhaust is turned waste into wealth, F-T synthesis raw material is obtained and utilizes more fully, improve the carbon utilisation rate of F-T synthesis gas.
The inventive method is specially adapted to the technique of fischer-tropsch product and the improvement to built technique such as F-T synthesis diesel oil, petroleum naphtha, especially with Fischer-Tropsch synthesis oil tail gas for raw material, obtain synthetic gas by steam reformation, F-T synthesis cyclostrophic is turned to unstripped gas and turns back in the production technique again utilized in F-T synthesis device.
The foregoing is only the optimal way of the embodiment of the present invention, the present invention is not limited to above-described embodiment, to those skilled in the art, the present invention can have various conversion and replacement, such as adopt the cycling and reutilization process of F-T synthesis waste gas in the Fischer-Tropsch synthesis of CO 2 reformation method or partial oxidation process, and by the method for the invention and other F-T synthesis waste gas combinationally uses or conbined usage promotes the process that F-T synthesis waste gas recycles.Therefore.Any amendment made under all principles in embodiment described in the inventive method and spirit, equivalent replacement, improvement etc., all belong to protection scope of the present invention.
Claims (10)
1. a Fischer-Tropsch process exhaust is converted into the method for F-T synthesis unstripped gas, comprise shortening, steam reformation and partial oxidation reaction, middle temperature water gas shift reation, waste heat recovery and gas-liquid separation four operations, it is characterized in that described shortening operation is by carrying out catalytic hydrogenation reaction in the hydrogenator that hydrogenation catalyst is housed, hydrogenation of unsaturated hydrocarbons in Fischer-Tropsch process exhaust is converted into stable hydrocarbon, described steam reformation and partial oxidation reaction operation comprise one-stage converter and secondary reformer two converters, the mixed gas that water vapour and the Fischer-Tropsch process exhaust through shortening form enters the one-stage converter that reforming catalyst A is housed and completes primary transformants, enter from one-stage converter gas out in the secondary reformer that reforming catalyst B is housed, pass in secondary reformer through the pure oxygen of preheating simultaneously and carry out a small amount of Fischer-Tropsch process exhaust oxidizing reaction and complete deep conversion, finally carry out water gas shift reation being equipped with in catalyzer to become in stove, described waste heat recovery and gas-liquid separation operation are that material water gas shift reation obtained is first through reclaiming heat, carry out gas-liquid separation again, gas phase is for meeting the unstripped gas of the hydrogen carbon proportioning required by F-T synthesis,
In described shortening operation, hydrogenation catalyst is JT-202;
The reforming catalyst A used in described one-stage converter is Z112-HA and Z112-HB, and wherein the weight ratio of Z112-HA and Z112-HB is 0.8-1.2:0.8-1.2;
Reforming catalyst B in described secondary reformer is CZ-7;
Catalyzer in described middle change stove is NB113.
2. a kind of Fischer-Tropsch process exhaust as claimed in claim 1 is converted into the method for F-T synthesis unstripped gas, and it is characterized in that in described shortening operation, service temperature is 220-250 DEG C, working pressure is 2.0-3.0MPa, and air speed is 1000-2000h
-1.
3. a kind of Fischer-Tropsch process exhaust as claimed in claim 1 is converted into the method for F-T synthesis unstripped gas, it is characterized in that the water carbon mol ratio of mixed gas in one-stage converter is 2.5-3.5:1.
4. a kind of Fischer-Tropsch process exhaust as claimed in claim 1 is converted into the method for F-T synthesis unstripped gas, and it is characterized in that in one-stage converter, service temperature is 650-850 DEG C, working pressure is 2.0-3.0MPa, and air speed is 1000-2000h
-1.
5. a kind of Fischer-Tropsch process exhaust as claimed in claim 1 is converted into the method for F-T synthesis unstripped gas, it is characterized in that described water vapour be temperature is 200 ~ 300 DEG C, pressure is the saturated vapor of 2.0 ~ 3.0MPa.
6. a kind of Fischer-Tropsch process exhaust as claimed in claim 1 is converted into the method for F-T synthesis unstripped gas, it is characterized in that the described oxygen through preheating enters secondary reformer, is 0.4-0.6 with the oxygen carbon mol ratio of two process transform furnace gas.
7. a kind of Fischer-Tropsch process exhaust as claimed in claim 1 is converted into the method for F-T synthesis unstripped gas, and it is characterized in that the service temperature in described secondary reformer is 850-1300 DEG C, working pressure is 2.0-3.0MPa, and air speed is 1000-2000h
-1.
8. a kind of Fischer-Tropsch process exhaust as claimed in claim 1 is converted into the method for F-T synthesis unstripped gas, and it is characterized in that the service temperature in described middle change stove is 340-360 DEG C, working pressure is 2.0-3.0MPa, and air speed is 1000-2000h
-1.
9. a kind of Fischer-Tropsch process exhaust as claimed in claim 1 is converted into the method for F-T synthesis unstripped gas, it is characterized in that described one-stage converter is outside equipped with double-pipe exchanger, partial heat is delivered to double-pipe exchanger by the high temperature two process transform gas coming from described secondary reformer, then carry out heat exchange by between the reactant in double-pipe exchanger and one-stage converter, thus provide thermal source for the reforming reaction in one-stage converter.
10. a kind of Fischer-Tropsch process exhaust as described in any one of claim 1-9 is converted into the method for F-T synthesis unstripped gas, it is characterized in that H in obtained F-T synthesis unstripped gas
2/ CO mol ratio is 2.9-3.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410366341.0A CN104150441B (en) | 2014-07-29 | 2014-07-29 | A kind of Fischer-Tropsch process exhaust is converted into the method for F-T synthesis unstripped gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410366341.0A CN104150441B (en) | 2014-07-29 | 2014-07-29 | A kind of Fischer-Tropsch process exhaust is converted into the method for F-T synthesis unstripped gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104150441A CN104150441A (en) | 2014-11-19 |
| CN104150441B true CN104150441B (en) | 2016-04-13 |
Family
ID=51876112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410366341.0A Active CN104150441B (en) | 2014-07-29 | 2014-07-29 | A kind of Fischer-Tropsch process exhaust is converted into the method for F-T synthesis unstripped gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104150441B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221720B (en) * | 2016-08-19 | 2018-03-13 | 武汉凯迪工程技术研究总院有限公司 | Selective catalytic oxidation converts the comprehensive utilization process of Fischer-Tropsch process exhaust |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190781A (en) * | 2006-11-23 | 2008-06-04 | 上海标氢气体技术有限公司 | Minitype light hydrocarbon steam reforming hydrogen manufacturing technique |
| CN102198931A (en) * | 2011-04-15 | 2011-09-28 | 庞玉学 | Method and device for co-producing hydrogen and synthesis gas by using dry gas |
| CN102838116A (en) * | 2012-09-10 | 2012-12-26 | 太原理工大学 | Method for preparing carbon monoxide from coke oven gas and carbon dioxide |
| CN103303866A (en) * | 2012-03-15 | 2013-09-18 | 上海汉兴能源科技有限公司 | Method for producing hydrogen or/and hydrogen-carbon monoxide synthesis gas by converting light dydrocarbon raw material |
-
2014
- 2014-07-29 CN CN201410366341.0A patent/CN104150441B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190781A (en) * | 2006-11-23 | 2008-06-04 | 上海标氢气体技术有限公司 | Minitype light hydrocarbon steam reforming hydrogen manufacturing technique |
| CN102198931A (en) * | 2011-04-15 | 2011-09-28 | 庞玉学 | Method and device for co-producing hydrogen and synthesis gas by using dry gas |
| CN103303866A (en) * | 2012-03-15 | 2013-09-18 | 上海汉兴能源科技有限公司 | Method for producing hydrogen or/and hydrogen-carbon monoxide synthesis gas by converting light dydrocarbon raw material |
| CN102838116A (en) * | 2012-09-10 | 2012-12-26 | 太原理工大学 | Method for preparing carbon monoxide from coke oven gas and carbon dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104150441A (en) | 2014-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20230234842A1 (en) | Chemical synthesis plant | |
| CN102838116B (en) | Method for preparing carbon monoxide from coke oven gas and carbon dioxide | |
| JPS5813482B2 (en) | I'm going to have a good time with this. | |
| CN100526273C (en) | Method for integral production of liquid ammonia and methanol and/or dimethyl ether by using coke oven gas as raw material | |
| CN103571541B (en) | A kind of co-production of methane and the catalysis gasification method of tar | |
| CN103979492A (en) | Technical method for preparation of synthetic gas by carbon dioxide-methane autothermal reforming | |
| RU2011101927A (en) | DEVICE AND METHODS FOR HYDROGEN AND CARBON MONOXIDE TREATMENT | |
| CN113396205B (en) | Carbon dioxide conversion engineering and system thereof | |
| CN103303863A (en) | Method for producing ammonia synthesis gas from coke-oven gas | |
| CN104937078A (en) | Hybrid plant for liquid fuel production and method for operating it where a gasification unit in the hybrid plant is operating at less than its design capacity or is not operational | |
| US20230174376A1 (en) | Production of Hydrocarbons | |
| RU2015102091A (en) | METHOD FOR FISCHER-TROPHE SYNTHESIS AND METHOD FOR USING WASTE GASES | |
| CN104709876A (en) | Process method for preparing synthesis gas by using zero carbon or negative carbon emission system | |
| US20230339747A1 (en) | Syngas stage for chemical synthesis plant | |
| CN104150441B (en) | A kind of Fischer-Tropsch process exhaust is converted into the method for F-T synthesis unstripped gas | |
| US9988586B2 (en) | Systems and methods for the use of Fischer-Tropsch tail gas in a gas to liquid process | |
| CN108408689B (en) | Anhydrous hydrogen production system | |
| CN110217757A (en) | Coal liquefaction, petroleum or the biomass equipment with the integration of higher carbon and the thermal efficiency are generated with reduced carbon dioxide | |
| RU2515477C2 (en) | Method of obtaining hydrogen | |
| CN214223794U (en) | Conversion and utilization system for discharged purge gas of device for preparing low-carbon mixed alcohol from synthesis gas | |
| WO2018032944A1 (en) | Comprehensive utilization process for selective catalytic oxidative conversion of tail gas from fischer-tropsch synthesis | |
| CN105347302B (en) | A kind of method of natural gas conversion production synthesis gas | |
| CN103569965A (en) | Hydrocarbon two-stage method for preparing synthesis gas through steam pure oxygen conversion | |
| CN112678771B (en) | Hydrogen production method and integrated system of SMR and methanol steam reforming | |
| CN103992198A (en) | Benzene production technology taking coke oven gas as raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |