JP2015007039A5

JP2015007039A5 -

Info

Publication number: JP2015007039A5
Application number: JP2014125647A
Authority: JP
Filing date: 2014-06-18
Publication date: 2017-06-22
Anticipated expiration: 2034-06-18

Claims

A method of simultaneously producing methanol and synthetic natural gas with coke oven gas, the method comprising:
(1) a step of pretreating at least one coke oven gas;
(2) adjusting the hydrogen / carbon ratio by adding at least one carbon-containing gas to the pretreated coke oven gas;
(3) compressing and desulfurizing the resulting mixed gas, and then performing a methanol synthesis reaction;
(4) separating the resulting methanol synthesis reaction product into a high methanol stream and a low methanol stream;
(5) subjecting the low methanol stream to a methane synthesis reaction in two or three methane synthesis reactors connected in series;
(6) A method comprising the step of producing synthetic natural gas by separating water from the resulting methane synthesis reaction product.

The method according to claim 1, wherein the carbon-containing gas is CO and / or CO ₂ .

The method of claim 2, wherein the carbon-containing gas is CO ₂ captured from flue gas emitted from a coker.

The mixed gas resulting from the carbon-containing gas is a hydrogen / carbon ratio of 2.2 to 2.7 [where the hydrogen / carbon ratio is (nH ₂ −nCO ₂ ) / (nCO + nCO ₂ ), and nH _2. The method according to claim 1, characterized in that it is added in such an amount that it has ₂ , nCO ₂ and nCO are the moles of H ₂ , CO ₂ and CO respectively.

The method according to claim 4, characterized in that the carbon-containing gas is added in such an amount that the resulting gas mixture has a hydrogen / carbon ratio of 2.45 to 2.5.

Perform the methane synthesis reaction by subjecting the low methanol stream to a water wash before sending it to two or three methane synthesis reactors connected in series, and sending the water wash stream to the methane synthesis reactor. The method of claim 1, wherein:

The process according to claim 1, characterized in that the methanol synthesis reaction is a once-through reaction and no methane steam conversion is carried out before the methanol synthesis reaction.

Three adiabatic methane synthesis reactors connected in series are used, where the inlet temperature of the first methane synthesis reactor is 250 ° C. to 350 ° C., and the outlet temperature of the first methane synthesis reactor is The process according to claim 1, characterized in that it is between 500 ° C and 680 ° C, and the second and third methane synthesis reactors operate at a lower temperature than the first methane synthesis reactor.

The process according to claim 1, characterized in that liquefied natural gas is produced by subjecting synthetic natural gas to cryogenic separation.

The method according to claim 1, wherein at least one Cu-based methanol synthesis catalyst is used in the methanol synthesis reaction, and at least one Ni-based methane synthesis catalyst is used in the methane synthesis reaction.

The methanol synthesis reaction is carried out in at least one fixed bed reactor, which is filled with at least one Cu-based methanol synthesis catalyst, the inlet temperature is 200-240 ° C., and the reaction pressure is 1. The method according to claim 1, wherein the method is operated under a condition of 5 to 9.0 MPa and a space velocity of 2000 to 12000 h ⁻¹ .

Using two methane synthesis reactors,
In the first methane synthesis reactor: at least one Ni-based methane synthesis catalyst is charged, the inlet temperature is 250 to 350 ° C., the pressure is 1.0 to 8.5 MPa, and the space velocity is 2000 to 15000 h. Using a fixed bed reactor operating at ^-1 conditions;
In the second methane synthesis reactor: at least one Ni-based methane synthesis catalyst is charged, the inlet temperature is 250 to 350 ° C., the pressure is 0.8 to 8.3 MPa, and the space velocity is 2000 to 10,000 h. ^Run on condition of ^-1 ;
The method according to claim 1, characterized in that the second methane synthesis reactor uses a fixed bed reactor which operates at a temperature lower than the operating temperature of the first methane synthesis reactor .

Using three methane synthesis reactors,
In the first methane synthesis reactor: at least one Ni-based methane synthesis catalyst is charged, the inlet temperature is 250 to 350 ° C., the pressure is 1.0 to 8.5 MPa, and the space velocity is 2000 to 15000 h. Using a fixed bed reactor operating at ^-1 conditions;
In the second methane synthesis reactor: at least one Ni-based methane synthesis catalyst is charged, the inlet temperature is 250 to 350 ° C., the pressure is 0.8 to 8.3 MPa, and the space velocity is 2000 to 10,000 h. Using a fixed bed reactor operating at ^-1 conditions;
In the third methane synthesis reactor: at least one Ni-based methane synthesis catalyst is charged, the inlet temperature is 250-350 ° C., the pressure is 0.7-8.2 MPa, and the space velocity is 2000-10000 h. Using a fixed bed reactor operating at ^-1 conditions;
The second methane synthesis reactor operates at a temperature lower than the operating temperature of the first methane synthesis reactor;
The method according to claim 1, wherein the third methane synthesis reactor is operated at a temperature lower than the operating temperature of the second methane synthesis reactor.

A plant for the simultaneous production of methanol and synthetic natural gas, wherein the plant is used in combination with at least one coker, wherein the plant comprises (1) at least one coke oven gas pretreatment unit, (2) at least one CO ₂ capture unit, (3) at least one compression and desulfurization unit, (4) at least one methanol synthesis unit, (5) at least one methane synthesis unit, and (6) optionally at least one Including two cryogenic separation units;
At least one inlet of the coke oven gas pretreatment unit is in communication with at least one coke oven gas outlet of the coker;
At least one inlet of the CO ₂ capture unit is in communication with at least one flue gas outlet of the coker;
At least one outlet of the CO ₂ capture unit and at least one outlet of the coke oven gas pretreatment unit are in communication with at least one inlet of the compression and desulfurization unit via at least one mixing device;
At least one outlet of the compression and desulfurization unit is in communication with at least one inlet of the methanol synthesis unit;
At least one outlet of the methanol synthesis unit is in communication with at least one inlet of the methane synthesis unit via at least one purifier;
A plant, wherein at least one outlet of the methane synthesis unit is optionally in communication with at least one inlet of the cryogenic separation unit.

The plant of claim 14, wherein the methanol synthesis unit comprises at least one methanol synthesis reactor and at least one methanol separator.

The plant of claim 15, wherein the methanol synthesis reactor is in the form of a fixed bed reactor.

The plant according to claim 15 or 16, wherein the methanol synthesis reactor is filled with at least one Cu-based methanol synthesis catalyst.

The plant according to claim 15, wherein the methanol separator comprises at least one gas-liquid separator and / or at least one rectification column.

The plant according to claim 15 or 16, wherein the methanol synthesis reactor is at least one once-through reactor.

The plant according to claim 14, 15 or 16, wherein the plant does not include any methane steam converter.

15. The plant of claim 14, wherein the methane synthesis unit comprises two or three methane synthesis reactors connected in series and at least one methane separator.

The plant of claim 21, wherein the methane synthesis reactor is in the form of a fixed bed reactor.

The plant of claim 21, wherein the methane synthesis reactors are the same or different.

The plant according to claim 21, wherein the methane synthesis reactor is packed with at least one Ni-based methane synthesis catalyst.