DE1913657B2 - PROCESS FOR CONTINUOUS PRODUCTION OF CARBON MONOXYDE - Google Patents

Description

Gas can be understood that has a methane content of ten scrubbing processes, such as ζ. Β, hot potash wash, at least 50 percent by volume. Suitable triethanolamine and monoethynolamine wash for nickel-containing catalysts can be used in both stages. The carbon dioxide-laden, nickel-containing caustic suitable for hydrocarbon splitting in the scrubbing solution is used via line 21 in the presence of steam (so-called steam) will. The hydrocarbon washer 17. The material-water vapor weight ratio in the output stripping steam required in the stripper 22 can be mixed in a manner known per se in the range between 1: 2 and 1: 4 through heat exchange with the line 14 gene, the starting mixture additionally being produced from 0.05 to 10 flowing hot gases. To simplify the flow diagram, 0.15 Nm ³ hydrogen-rich gas per kg used, the hydrocarbon required for this is included. The carbon-gold heat exchanger has not been drawn in. Oxide addition to the rich gas is in the range between The carbon dioxide produced in the expeller 22 and 6 Nm * CO ₂ per kg of hydrocarbon used reaches the line 12 via the line 24, via the substance. The reaction temperature is in the first 15 - as described above - in the Reich stage 350 to 500 ° C and in the second stage 600 gas stream is fed.

up to 900 ° C, with both stages, as already said, because the amount of carbon dioxide produced is the was, can be operated under increased pressure is not able to meet the needs of the process nen. The conversion of the rich gas in the second stage is that of heating the tubular gap furnace 10 takes place in a so-called tube gap furnace, 20 falling flue gas also a carbon dioxide subjected by burning desulphurized coal scrubbing. It is before entering hydrogen. Residual gas which, however, is required in the carbon monoxide scrubbing process application occurs, and / or hydrogen is heated. Flue gas containing oxygen with the addition of In this case, the carbon hydrogen must be burned for combustion. The flue gas becomes dalen hydrogen are desulphurized, because this is done by 25 through the line 25 via the heat exchanger Accruing flue gas after exiting from the 16, 6, 26 and 3 to the incinerator 27 ge tubular gap furnace for the purpose of carbon dioxide production. The required amount of hydrogen is over is subjected to a carbon dioxide wash. The line 28 is supplied. From there that comes from The carbon dioxide obtained in this way serves to cover the flue gas via line 29 to the carbon dioxide Carbon dioxide requirement of the 30 washer 30 according to the invention. Because of the low CO., - partial pressure Procedure. The still missing amount of carbon dioxide in the flue gas flow, it is advisable to use the carbon dioxide from the second stage (tubular fissure oxide washer 30 with monoethanolamine solution oven) emigas rich in carbon monoxide. The flue gas freed from carbon dioxide severed. For this purpose, it is also expedient to fall into the exhaust gas chimney 32 via the line 31 a carbon dioxide wash applied. 35 heads. The washing solution loaded with carbon dioxide

The method according to the invention is intended to reach the abortion 34 in the line 33 on the basis of the.

In the flow chart shown in the drawing, carbon dioxide is still driven via line 35

are explained in more detail, and for a better overview also fed into the line 12 and so with

only the carbon dioxide coming from the aborter 22 to carry out the process

necessary system parts are reproduced. 40 stream united. The regenerated wash solution will

The hydrocarbon to be used flows through the line 36 back to the top of the carbon line 1 via the heat exchangers 2 and 3 into the lendiuxyd washer 30.
Desulphurisation 4. The desulphurized hydrocarbon coming from the desulphurisation plant 19 ends up in falling hydrogen to be valued. If the latter is the case, then the desulphurized hydrocarbon is branched off and the next is split into two substreams. The burner supply lines 9 of the tubular gap furnace provided for via the line 8 and the heat exchanger 2 to the heating of the tubular gap furnace 10 is thereby conveyed via the line 37 in

10 arrives. This subset of the desulphurized coal 50 is fed into the burner supply lines 38. Of the Hydrogen is used to heat the tube; the other part of the hydrogen enters the pipe cracking furnace 10 burned. The one from the Reichgasrea 39. From this line branch off: Line 28, rich gas exiting gate 7 reaches the pipe through the - as already mentioned - the

11 and the heat exchanger 16 to the tubular gap furnace. Combustion device 27 required hydrogen supplied required amount of carbon dioxide is through the 55 is leads, furthermore the line 40, through which the for Line 12 fed into the rich gas stream. In the desulfurization of the starting hydrocarbon with a nickel-containing catalyst filled cans required hydrogen is added, as well as the 13 of the tubular gap furnace 10 finds the conversion line 41, through which the for the first stage of the Verin the relatively carbon monoxide-rich end gas takes place. driving (rich gas production) required water-this passes through the line 14 via which the amount of waste 60 is added.

heat boiler 15 to the carbon dioxide scrubber 17. The one required for the production of rich gas End gas freed from carbon dioxide is finally water vapor can be withdrawn from the waste heat boiler 15 the line 18 to the cryogenic decomposition plant and via the line 42 and the heat exchanger 19, in which it is fed into its component parts shear 26 to the petrol used. By will lay. The thereby separated carbon monoxide 65 the line 43 can finally residual gas that at the carbon monoxide is obtained through the line 20 to the consumption points, in which by the guided. Line 37 to the tubular gap furnace 10 flowing in the carbon dioxide scrubber 17, the known hydrogen stream can be fed.

5 6

The practical usefulness of the CO ₂ according to the invention 39.2 percent by volume

The method should be based on the following figure: CO 33.7 percent by volume

len example, which relates to the splitting of gasoline, de- H ₂ 26.4 percent by volume

be protested. The mixing ratio of the in the CH ₄ 0.7 percent by volume

Rich gas reactor 7 entering reaction mixture 5

is as follows: This gas is in the carbon dioxide washer 17

1 kg of gasoline, discharged under a pressure of 14 ata and

O 07 Nm ³ hydrogenation gas, i ^ ^{e e} IOER temperature of 100 to 120 ° C operated

2 ^ 5 kg of steam. will. The practically occurring through line 18

lo table carbon dioxide-free gas has the following combinations

The following reaction set-up prevails in the rich gas reactor:

conditions: CO ₂ 0.1 percent by volume

Pressure 19 ata CO 55.4 percent by volume

Temperature 400 to 450 ° CH ₂ 43.4 percent by volume

¹⁵ CH,. . 1.1 percent by volume

The rich gas exiting through line 11 has ⁴

the following composition: This gas enters the low-temperature decomposition

CO ₂ 22.0 volume percent generation system 19. The carbon monoxide separated there

CO 0.4 volume percent oxide has a purity of 98 volume percent.

Η, 15 0 percent by volume ^{ao In} addition, it also contains 2 percent by volume H ₂ -h CH ₄ .

Qj g2 * 6 percent by volume ^The carbon dioxide washer 30 is under gentle

⁴ ' ^p overpressure operated. Its operating temperature is

Before it enters the tubular gap furnace 10, it is at 30 to 40 ° C. The flue gas has before it enters

the following composition of the rich gas through the line 12 4.2Nm ⁸ CO _{2 in this scrubber:}

added. In the cans 13 of the tubular _{gap * 5 co n 8} percent by volume

Oven 10, the following reaction conditions prevail: _N ² 88.2 percent by volume

ι JnI eic "| ^ 3t 3

Temperature ''.'.'.'.'.'.'.'.'.'.'.'.'.'. 650 to 850 ° C ^ as flue gas passed through the exhaust chimney 32

contains only 0.7 percent by volume of CO _{2 in} addition to 99.3

The end gas exiting through line 14 has 30 percent by volume N ₂ . The following composition obtained from the flue gas: CO ₂ amount is 1.2 Nm ^s .

1 sheet of drawings

Claims (4)

In this case, the addition of oxygen is measured in such a way that the catalytic combustion is maintained to the extent necessary to provide the necessary tub through which the water 1. Process for the continuous generation 5 gas equilibrium called equilibrium reaction of carbon monoxide by catalytic cleavage shifted entirely to the side of the carbon monoxide of hydrocarbons, thereby being identified. Ax this way, the occurrence of coals is supposed to show that a mixture of desulphurized dioxide is suppressed in the second fission stage of the process system gaseous or liquid hydrocarbons. with a boiling point of up to 220 ° C, water vapor io In contrast, the present invention and a hydrogen-rich gas in a first generation aims to create a process that Stage in the presence of a nickel-containing catalyst - not only to the use of methane or Erdsators is bound in a well-known manner in a suction gas, but also the use The so-called rich gas is split, whereupon the so different produced gaseous or liquid hydrocarbons Rich gas is permitted after the addition of carbon dioxide with a boiling point of up to 220 ° C. as oxide in a second stage in the presence of an example are refinery gas, liquefied petroleum gas and nickel-containing catalyst in a so-called gasoline Tube fission furnace, which is produced by burning desulphurized hydrocarbon, residual gas and / drive for the continuous production of carbon dioxide Hydrogen is heated into a relatively carbon monoxide by catalytic cleavage of carbon monoxide End gas is converted to hydrogen, which is characterized in that from which the carbon monoxide to be obtained is a mixture of desulphurized gaseous or by low temperature decomposition of the remaining liquid hydrocarbons with a boiling point up to Gas components is separated. 220 ° C, steam and a hydrogen are enough 2. The method according to claim 1, characterized ge 25 gas in a first stage in the presence of a nickel, that the catalyst containing its implementation in a known manner in Required carbon dioxide from which a so-called rich gas is split during the heating process, whereupon the When the tubular gap furnace was used (second stage), rich gas was generated after the addition of carbon dioxide lenden flue gas and from the relatively carbon-rich in a second stage in the presence of a nickel-containing monoxide End gas is separated. 30 gene catalyst in a so-called tube gap 3. The method according to claims 1 and 2, furnace made by incineration of desulphurized characterized in that as hydrogen-free hydrocarbon, residual gas and / or hydrogen beches Gas (first stage) a subset of which is heated in a relatively carbon monoxide-rich end low-temperature decomposition accruing hydrogen gas is converted, from which the to be extracted Fraction is used. 35 carbon monoxide by cryogenic decomposition of 4. The method according to claims 1 to 3, that the remaining gas components are separated off,
characterized in that both stages are operated under the increased pressure according to the invention. Process required carbon dioxide can thereby the one when heating the tubular fission furnace (second 40 level) accruing flue gas as well as from the relative carbon monoxide-rich end gas are separated. As a hydrogen-rich gas to carry out the In the first cleavage stage, a subset of the hydrogen-45 produced in the low-temperature decomposition can be used Fraction are used. The method according to the invention can be used in The present invention relates to a process operated in both stages under increased pressure for the continuous production of carbon monoxide. by catalytic cleavage of hydrocarbons, The peculiarities of the inventive method whereby the method according to the invention in particular makes it necessary that the used the production of carbon monoxide in technical hydrocarbons has to be desulfurized beforehand should enable. sen. The desulfurization can be carried out in a known manner It is known that gas containing carbon monoxide can be produced by hydrogenation of the organic sulfur compound mixtures in such a way that methane is fertilized from the starting hydrocarbon to form hydrogen or a methane-rich starting hydrocarbon, the material for this purpose, especially natural gas, in the presence Known hydrogenation catalysts can be used by carbon dioxide on a cobalt molybdate catalyst. Assuming a liquid outlet at a temperature between 425 and 870 ° C, cleavage. hydrocarbon, such as B. gasoline, so the further is in the French patent first cleavage stage, a subset of the 951 a process for generating a as 60 prior condensation by stripping or by oxo synthesis gas designated mixture of carbon monoxide and absorption on a suitable absorption mass Hydrogen described. Doing so will be removed. If, on the other hand, a gas in the first stage is natural gas in the presence of water-like starting hydrocarbons, such as. If, for example, earth vapor is catalytically converted into a hydrogen-rich gas, the hydrogen sulfide that is formed can split up, and the carbon oxides and the carbon oxides can only be removed by absorption. It may contain small amounts of methane. This fission gas, which can be regenerated or not regenerated, will then be used in the presence of a mixture of cohesive masses,
Lendioxyd and oxygen further converted. The sub Reichgas in this context is intended to be a