Title of Invention	A PROCESS FOR PREPARATION OF A HYDROGEN AND CARBON MONOXIDE RICH GAS BY CATALYTIC AUTOTHERMAL REFORMING
Abstract	A process for preparation of a hydrogen and carbon monoxide rich gas by catalytic autothermal reforming of a hydrocarbon feedstock containing higher hydrocarbons in an autothermal reformer comprising the steps of (a)passing the hydrocarbon feedstock through a reactor containing steam reforming catalyst to remove or reduce the contents of higher hydrocarbons in the hydrocarbon feedstock; (b) passing the effluent from the fIrst reactor to an autothermal reformer; and (c) withdrawing from the autothermal reformer a product gas rich in hydrogen and carbonmonoxide.

Title of Invention

A PROCESS FOR PREPARATION OF A HYDROGEN AND CARBON MONOXIDE RICH GAS BY CATALYTIC AUTOTHERMAL REFORMING

Abstract

A process for preparation of a hydrogen and carbon monoxide rich gas by catalytic autothermal reforming of a hydrocarbon feedstock containing higher hydrocarbons in an autothermal reformer comprising the steps of (a)passing the hydrocarbon feedstock through a reactor containing steam reforming catalyst to remove or reduce the contents of higher hydrocarbons in the hydrocarbon feedstock; (b) passing the effluent from the fIrst reactor to an autothermal reformer; and (c) withdrawing from the autothermal reformer a product gas rich in hydrogen and carbonmonoxide.

Full Text	The present invention is directed to soot free autothermal reforming (ATR) of hydrocarbon feed containing higher hydrocarbons. In the autothermal reforming, combustion of hydrocarbon feed is carried out with substoichiometric amounts of oxygen by flame reactions in a burner combustion zone and, subsequently, steam reforming of the partially combusted feedstock in a fixed bed of steam reforming catalyst. Substoichiometric combustion of hydrocarbons leads disad-vantageously to formation of soot. Soot formation may be .avoided by using a specific burner design and through controlling the operating conditions of the ATR process. Soot is formed in the flame of an autothermal reactor within certain ranges of operating conditions. When the amount of steam relative to the other components send to the ATR reactor is under a critical value, soot is formed in the reacting feed. One such burner useful in ATR is described in U.S. Patent No. 5,496,170. The limiting amount of steam can be expressed as the critical steam to carbon ratio, which is the molar feed flow rate of steam to the molar flow rate of carbon in the hydrocarbon feed. The hydrocarbon feedstocks can be in form of natural gas or hydrocarbon including LPG, butane, naphtha, etc. The molar flow rate of carbon is calculated as the molar flow rate of the hydrocarbon times the carbon contents of the hydrocar¬bon. Examples of operation conditions, which do not result in soot formation, are summarized in a paper by Christensen and Primdahl (Hydrocarbon processing, March 1994, pages 39-46), Those conditions are shown in Table 1. The tests have been conducted in a pilot plant. Due to heat loss from the relatively small pilot unit, the ©diabatic ATR exit tem¬perature will be higher than the measured ATR exit tempera¬ture. This means that if a large unit, from which the heat loss is negligible, is subjected to the exact same operat¬ing conditions, the ATR exit temperature will be close to the adiabatic ATR exit temperature. The soot precursors are formed in the combustion zone of the ATR. Most of the heat loss occurs after the combustion zone. A subsequent heat loss cannot have any influence on the reactions in the * combustion zone. The oxygen to carbon ratio (O2/C) is also shown in Table 1. The definition of this ratio is analogue to the steam to carbon ratio, however, with steam substi¬tuted by oxygen. The exit temperature from the ATR reactor ..can be calculated from the O2/C ratio, when the heat loss from the reactor is known. Operation conditions which do not result in soot formation (from Christensen and Primdahl, 1994) Advantageously, the process is operated at low steam to carbon ratios, since a low ratio lowers the investment expenses for an ATR plant and reduces the necessary energy consumption in operating the plant. Additionally, a low steam to carbon ratio makes it possible to optimize the produced synthesis gas composition for production of CO-rich gases for e.g. methanol or dimethyl ether synthesis and Fischer-Tropsch processes. It has been found that arranging a low temperature reform¬ing reactor with steam reforming catalyst upstream the autothermal reformer reduces the critical steam to carbon ratio. The steam reforming reactor removes or reduces the content of higher hydrocarbons. Higher hydrocarbons are hydrocarbons that consist of two or more carbon atoms. The steam reforming catalyst will convert the higher hydro¬carbons to a mixture of methane, carbonmonoxide, carbon-dioxide and hydrogen. ■ The low temperature steam reforming reactor can be an adiabatic prereformer or a heated prereformer, e,g- in form of a catalyzed heat exchanger coil as described in European Patent Publication No. 855,366. The exit temperature of an effluent stream from the low temperature steam reforming reactor is not higher than 600^C. Accordingly, this invention provides a process for the preparation of a hydrogen and/or carbonmonoxide rich gas by catalytic autothermal reforming of a hydrocarbon feedstock in an autothermal reformer comprising further steps of: (a) passing the hydrocarbon feedstock through a first reactor containing steam reforming catalyst to substan¬ tially remove the content of higher hydrocarbons in the hydrocarbon feedstock; (b) passing the effluent from the first reactor to an autothermal reformer; and (c) withdrawing from the autothermal reformer a product gas rich in hydrogen and carbonmonoxide. As an advantage of the invention dt will be possible to operate the autothermal reactor at lower steam to carbon ratio than when using the unconverted feed stream as feed for the autothermal reformer. As a second advantage, it is possible to preheat the feed gas for the ATR to a higher temperature when it contains no higher hydrocarbon. This results in a lower oxygen consump¬tion by the process. The invention is in particular useful in the steam reform¬ing of accociated gas. Associated gas is natural gas pro¬duced during oil production. This gas is usually flared at the drilling rig, since it is not economical to ship asso¬ciated gas. Associated gas has a high content of higher hydrocarbons. Example 1 The test unit consists of a system for providing the feeds to the ATR reactor, the ATR reactor and equipment for post treatment of the product gas. The feed streams consist of natural gas, steam, oxygen, hydrogen and optionally butane. The composition of the natural gas is given in Table 2. All gases are compressed to the operating pressure and preheated to the operating temperature. The natural gas is desulphurized before enter¬ing the ATR reactor. The feeds are combined into two streams and send to the burner of the ATR. A first feed stream contains natural gas, hydrogen, steam, and optional¬ly butane. This feed stream is heated to 500^C. The other feed stream contains oxygen and steam and is heated to 220'^C. The pressure in the ATR reactor is 2.46 MPa. Option¬ally, the natural gas containing stream is passed through a prereformer before entering the ATR reactor. Also in this case, the gas stream is heated to 500^C before entering the ATR reactor. Table 2 Component Mole fraction % N^ 0.42 COi 1,16 CH4 94,55 2.75 0,70 C4 0.31 c,^ 0,11 Composition of natural gas In the ATR reactor, the substoichiometric combustion and subsequent catalytic steam reforming and shift reactions are carried out. The inlet and exit gas compositions are measured by gaschromatography. Downstream the ATR reactor, the product gas is cooled and the majority of the steam content of the product gas is condensed- If soot is formed, it is captured in the conden¬sate. The condensate is subjected to both gravimetric and spectrophotometric examinations. The following tests were carried out to demonstrate the influence of passing the feed gas through a prereformer. one test the feed gas was doped with butane. The butane concentration was 4.0 vol% of the total hydrocarbon. In Each test was made by approaching the critical steam to carbon ratio from the steam rich side. The tests were initiated with a sufficiently high steam flow to ensure soot free conditions. The steam Slow was then decreased in steps. The system was allowed to become stable, after which the condensate was examined for soot content. If the con¬densate was still soot free, the next step was taken. Term "soot free conditions" refers to condition in which the soot formation is negligible. The soot amount formed at the critical steam to carbon ratio is approximately 3-5 ppm. The carbon flow rates were in the below described tests 100-103 Nm-^/h, The hydrogen flow rate was 2 Nm-^/h, The steam flow was adjusted to obtain the given steam to carbon ratio. The oxygen flow rate was adjusted to obtain the desired operating temperature in the range from 55 to 58 Nm^/h. Due to heat loss from the relatively small pilot, the adiabatic ATR-exit temperature will be higher than the temperature given in Table 3. A large industrial unit will be very close to adiabatic condition and the exit tempera¬ture from such a unit will, hence, be very close to the adiabatic given in Table 3 when the industrial unit other¬wise is operated at exactly the same conditions as quoted in Table 3. The composition of the product gate from the ATR reactor in the tests of Table 3 was measured by gaschromatography. The gas compositions are shown in Table 4. Gas composition is given as dry mole percentage, which is the mole composition of the gas components when steam is not included. Table 4 Teat No H2 N2 CO CO2 CH4 % % % % % 1,1 64.4 0,14 26.74 6.81 1.87 1.2 65,1 0.12 25.17 6.99 2,62 1.3 64.5 0,12 26,09 7.67 1.62 1 Composition of product gas (dry mole%) of the test of Table 3 It is seen from Table 3, when passing the feed steam through a prereformer the critical steam to carbon ratio decreases. Furthermore, it is shown that an increased content of butane in the feed gas to the ATR causes the critical steam to carbon ratio to increase. This means that the advantage of passing the feed through a prereformer will increase, if the feed contains larger amount of higher hydrocarbon. Example 2 The same test unit as in Example 1 was used Ethane or butane is added to the natural gas containing feed stream in test run 2 and 3. The carbon flow rates were in the below described tests 102-103 Nm-^/h. The hydrogen flow rate was 3 Nm^/h. The steam flow was adjusted to obtain the given steam to carbon ratio. The oxygen flow rate was adjusted to obtain the desired operating temperature anci was in the interval 58-60 Nm The composition of the product gas from the ATR reactor in the tests of Table 5 are shown in Table 6. Composition of product gas (dry mole%) of the tests of Table 5 It is seen from Table 5 that a higher content of both ethane and butane causes the critical steam to carbon ratio to increase. CLAIMS 1. Process for preparation of a hydrogen and/or carbon monoxide rich gas by catalytic autothermal reforming of a hydrocarbon feedstock containing higher hydrocarbons in an autothermal reformer comprising the further steps of (a) passing the hydrocarbon feedstock through a reactor containing steam reforming catalyst to remove or reduce the contents of higher hydrocarbons in the hydrocarbon feedstock; (b) passing the effluent from the first reactor to an autothermal reformer; and (c) withdrawing from the autothermal reformer a product gas rich in hydrogen and carbon monoxide• 2. Process of claim 1, wherein the hydrocarbons feedstock is natural gas and/or associated gas. 3. Process of claim 1 or 2, wherein the first reactor is adiabatically operated. 4 • Process according to anyone of the preceding claims, wherein the temperature at outlet of the first reactor is below 600°C, 5. Process for preparation of a hydrogen and/or carbon monoxide substantially as herein described and exemplified.

Full Text

The present invention is directed to soot free autothermal reforming (ATR) of hydrocarbon feed containing higher hydrocarbons.
In the autothermal reforming, combustion of hydrocarbon feed is carried out with substoichiometric amounts of oxygen by flame reactions in a burner combustion zone and, subsequently, steam reforming of the partially combusted feedstock in a fixed bed of steam reforming catalyst. Substoichiometric combustion of hydrocarbons leads disad-vantageously to formation of soot. Soot formation may be .avoided by using a specific burner design and through controlling the operating conditions of the ATR process. Soot is formed in the flame of an autothermal reactor within certain ranges of operating conditions. When the amount of steam relative to the other components send to the ATR reactor is under a critical value, soot is formed in the reacting feed. One such burner useful in ATR is described in U.S. Patent No. 5,496,170. The limiting amount of steam can be expressed as the critical steam to carbon ratio, which is the molar feed flow rate of steam to the molar flow rate of carbon in the hydrocarbon feed. The hydrocarbon feedstocks can be in form of natural gas or hydrocarbon including LPG, butane, naphtha, etc. The molar flow rate of carbon is calculated as the molar flow rate of the hydrocarbon times the carbon contents of the hydrocar¬bon.
Examples of operation conditions, which do not result in soot formation, are summarized in a paper by Christensen and Primdahl (Hydrocarbon processing, March 1994, pages 39-46), Those conditions are shown in Table 1. The tests have been conducted in a pilot plant. Due to heat loss from the

relatively small pilot unit, the ©diabatic ATR exit tem¬perature will be higher than the measured ATR exit tempera¬ture. This means that if a large unit, from which the heat loss is negligible, is subjected to the exact same operat¬ing conditions, the ATR exit temperature will be close to the adiabatic ATR exit temperature. The soot precursors are formed in the combustion zone of the ATR. Most of the heat loss occurs after the combustion zone. A subsequent heat loss cannot have any influence on the reactions in the * combustion zone. The oxygen to carbon ratio (O2/C) is also shown in Table 1. The definition of this ratio is analogue to the steam to carbon ratio, however, with steam substi¬tuted by oxygen. The exit temperature from the ATR reactor ..can be calculated from the O2/C ratio, when the heat loss from the reactor is known.

Operation conditions which do not result in soot formation (from Christensen and Primdahl, 1994)
Advantageously, the process is operated at low steam to carbon ratios, since a low ratio lowers the investment expenses for an ATR plant and reduces the necessary energy consumption in operating the plant. Additionally, a low steam to carbon ratio makes it possible to optimize the

produced synthesis gas composition for production of CO-rich gases for e.g. methanol or dimethyl ether synthesis and Fischer-Tropsch processes.
It has been found that arranging a low temperature reform¬ing reactor with steam reforming catalyst upstream the autothermal reformer reduces the critical steam to carbon ratio. The steam reforming reactor removes or reduces the content of higher hydrocarbons. Higher hydrocarbons are hydrocarbons that consist of two or more carbon atoms. The steam reforming catalyst will convert the higher hydro¬carbons to a mixture of methane, carbonmonoxide, carbon-dioxide and hydrogen.
■ The low temperature steam reforming reactor can be an adiabatic prereformer or a heated prereformer, e,g- in form of a catalyzed heat exchanger coil as described in European Patent Publication No. 855,366. The exit temperature of an effluent stream from the low temperature steam reforming reactor is not higher than 600*^C.
Accordingly, this invention provides a process for the preparation of a hydrogen and/or carbonmonoxide rich gas by catalytic autothermal reforming of a hydrocarbon feedstock in an autothermal reformer comprising further steps of:
(a) passing the hydrocarbon feedstock through a first
reactor containing steam reforming catalyst to substan¬
tially remove the content of higher hydrocarbons in the
hydrocarbon feedstock;
(b) passing the effluent from the first reactor to an autothermal reformer; and
(c) withdrawing from the autothermal reformer a product gas rich in hydrogen and carbonmonoxide.

As an advantage of the invention dt will be possible to operate the autothermal reactor at lower steam to carbon ratio than when using the unconverted feed stream as feed for the autothermal reformer.
As a second advantage, it is possible to preheat the feed gas for the ATR to a higher temperature when it contains no higher hydrocarbon. This results in a lower oxygen consump¬tion by the process.
The invention is in particular useful in the steam reform¬ing of accociated gas. Associated gas is natural gas pro¬duced during oil production. This gas is usually flared at the drilling rig, since it is not economical to ship asso¬ciated gas. Associated gas has a high content of higher hydrocarbons.
Example 1
The test unit consists of a system for providing the feeds to the ATR reactor, the ATR reactor and equipment for post treatment of the product gas.
The feed streams consist of natural gas, steam, oxygen, hydrogen and optionally butane. The composition of the natural gas is given in Table 2. All gases are compressed to the operating pressure and preheated to the operating temperature. The natural gas is desulphurized before enter¬ing the ATR reactor. The feeds are combined into two streams and send to the burner of the ATR. A first feed stream contains natural gas, hydrogen, steam, and optional¬ly butane. This feed stream is heated to 500*^C. The other feed stream contains oxygen and steam and is heated to 220'^C. The pressure in the ATR reactor is 2.46 MPa. Option¬ally, the natural gas containing stream is passed through a

prereformer before entering the ATR reactor. Also in this case, the gas stream is heated to 500*^C before entering the ATR reactor.
Table 2

Component

Mole fraction %

N^

0.42

COi

1,16

CH4

94,55

2.75
0,70

C4

0.31

c,^

0,11

Composition of natural gas
In the ATR reactor, the substoichiometric combustion and subsequent catalytic steam reforming and shift reactions are carried out. The inlet and exit gas compositions are measured by gaschromatography.
Downstream the ATR reactor, the product gas is cooled and the majority of the steam content of the product gas is condensed- If soot is formed, it is captured in the conden¬sate. The condensate is subjected to both gravimetric and spectrophotometric examinations.

The following tests were carried out to demonstrate the influence of passing the feed gas through a prereformer. one test the feed gas was doped with butane. The butane concentration was 4.0 vol% of the total hydrocarbon.

In

Each test was made by approaching the critical steam to carbon ratio from the steam rich side. The tests were initiated with a sufficiently high steam flow to ensure

soot free conditions. The steam Slow was then decreased in steps. The system was allowed to become stable, after which the condensate was examined for soot content. If the con¬densate was still soot free, the next step was taken. Term "soot free conditions" refers to condition in which the soot formation is negligible. The soot amount formed at the critical steam to carbon ratio is approximately 3-5 ppm.
The carbon flow rates were in the below described tests 100-103 Nm-^/h, The hydrogen flow rate was 2 Nm-^/h, The steam flow was adjusted to obtain the given steam to carbon ratio. The oxygen flow rate was adjusted to obtain the desired operating temperature in the range from 55 to 58 Nm^/h.
Due to heat loss from the relatively small pilot, the adiabatic ATR-exit temperature will be higher than the temperature given in Table 3. A large industrial unit will be very close to adiabatic condition and the exit tempera¬ture from such a unit will, hence, be very close to the adiabatic given in Table 3 when the industrial unit other¬wise is operated at exactly the same conditions as quoted in Table 3.

The composition of the product gate from the ATR reactor in the tests of Table 3 was measured by gaschromatography. The gas compositions are shown in Table 4. Gas composition is given as dry mole percentage, which is the mole composition of the gas components when steam is not included.
Table 4

Teat No H2 N2 CO CO2 CH4
% % % % %
1,1 64.4 0,14 26.74 6.81 1.87
1.2 65,1 0.12 25.17 6.99 2,62
1.3 64.5 0,12 26,09 7.67 1.62 1
Composition of product gas (dry mole%) of the test of Table 3
It is seen from Table 3, when passing the feed steam through a prereformer the critical steam to carbon ratio decreases. Furthermore, it is shown that an increased content of butane in the feed gas to the ATR causes the critical steam to carbon ratio to increase. This means that the advantage of passing the feed through a prereformer will increase, if the feed contains larger amount of higher hydrocarbon.
Example 2
The same test unit as in Example 1 was used* Ethane or butane is added to the natural gas containing feed stream in test run 2 and 3.
The carbon flow rates were in the below described tests 102-103 Nm-^/h. The hydrogen flow rate was 3 Nm^/h. The steam flow was adjusted to obtain the given steam to carbon ratio. The oxygen flow rate was adjusted to obtain the

desired operating temperature anci was in the interval 58-60 Nm

The composition of the product gas from the ATR reactor in the tests of Table 5 are shown in Table 6.

Composition of product gas (dry mole%) of the tests of Table 5
It is seen from Table 5 that a higher content of both ethane and butane causes the critical steam to carbon ratio to increase.

CLAIMS
1. Process for preparation of a hydrogen and/or carbon monoxide rich gas by catalytic autothermal reforming of a hydrocarbon feedstock containing higher hydrocarbons in an autothermal reformer comprising the further steps of
(a) passing the hydrocarbon feedstock through a reactor
containing steam reforming catalyst to remove or reduce the
contents of higher hydrocarbons in the hydrocarbon
feedstock;
(b) passing the effluent from the first reactor to an autothermal reformer; and
(c) withdrawing from the autothermal reformer a product gas rich in hydrogen and carbon monoxide•

2. Process of claim 1, wherein the hydrocarbons feedstock is natural gas and/or associated gas.
3. Process of claim 1 or 2, wherein the first reactor is adiabatically operated.
4 • Process according to anyone of the preceding claims, wherein the temperature at outlet of the first reactor is below 600°C,

5. Process for preparation of a hydrogen and/or carbon monoxide substantially as herein described and exemplified.

Documents:

921-mas-1999-abstract.pdf

921-mas-1999-claims filed.pdf

921-mas-1999-claims granted.pdf

921-mas-1999-correspondnece-others.pdf

921-mas-1999-correspondnece-po.pdf

921-mas-1999-description(complete)filed.pdf

921-mas-1999-description(complete)granted.pdf

921-mas-1999-form 1.pdf

921-mas-1999-form 26.pdf

921-mas-1999-form 3.pdf

921-mas-1999-form 5.pdf

921-mas-1999-other documents.pdf

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Patent Number

214012

Indian Patent Application Number

921/MAS/1999

PG Journal Number

13/2008

Publication Date

31-Mar-2008

Grant Date

23-Jan-2008

Date of Filing

17-Sep-1999

Name of Patentee

HALDOR TOPSOE A/S

Applicant Address

NYMOLLEVEJ 55, DK-2800 LYNGBY,

Inventors:

#	Inventor's Name	Inventor's Address
1	THOMAS SANDAHL CHRISTENSEN	KULSVIERTOFTER 52, DK-2800 LYNGBY,

PCT International Classification Number

C01 B 3/38

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	PA1998 01211	1998-09-25	Denmark