Process for producing chlorine from HCL
A process is described for the production of chlorine by a catalysed gas-phase oxidation of hydrogen chloride with an oxygen-containing gas stream.
1. A process for the production of chlorine by a catalysed gas phase oxidation of hydrogen chloride with an oxygen-containing gas stream, consisting of the process stages:
a) compressing a hydrogen chloride stream ( 1 ) in an HCl compression step ( 30 ) to an elevated pressure to obtain a compressed hydrogen chloride stream ( 2 );
b) purifying the compressed hydrogen chloride stream ( 2 ) in an HCl gas purification step ( 31 ) to obtain a purified hydrogen chloride stream ( 3 );
c) combining an oxygen-containing return stream ( 16 ) with the purified hydrogen chloride stream ( 3 ) to form a feedstock stream ( 4 );
d) introducing the feedstock stream ( 4 ) into an oxidation zone ( 32 ), in which hydrogen chloride and oxygen are partially reacted, in the presence of a catalyst, to form chlorine and water, and a product stream ( 5 ), containing chlorine, oxygen, hydrogen chloride and water, is obtained;
e) introducing the product stream ( 5 ) into a process step ( 33 ) for the separation of hydrogen chloride and water in the form of aqueous hydrochloric acid ( 6 ) from the product stream ( 5 ) to obtain a product stream ( 7 );
f) introducing the product stream ( 7 ) at least partly freed from hydrogen chloride and water into a drying step ( 34 ) for further drying with a reduction of the proportion of water in the product stream ( 7 );
g) introducing the dried gas stream ( 8 ) obtained from the drying step ( 34 ) into a chlorine compression step ( 35 ) to increase the pressure of the gas stream ( 8 ) with the formation of a compressed gas stream ( 9 );
h) introducing the compressed gas stream ( 9 ) into a separation step ( 36 ) for the at least partial separation of the chlorine ( 10 ) contained in the gas ( 9 ) with the formation of a gas stream ( 11 ), which contains unreacted oxygen;
i) introducing at least a portion of gas stream ( 11 ) remaining after the chlorine separation ( 36 ) into a gas-washing process step ( 38 ) to form a purified stream ( 14 ), a partial stream ( 12 ) of the gas stream ( 11 ) being discharged between the chlorine separation ( 36 ) and the gas-washing step ( 38 ) or downstream of the gas-washing step ( 38 );
j) introducing the discharged partial gas stream ( 12 ) into a waste gas treatment step ( 37 );
k) combining the stream ( 14 ) coming out of the gas-washing step ( 38 ), containing unreacted oxygen, with a stream ( 15 ) containing fresh oxygen to form an oxygen-containing return stream ( 16 );
l) returning the return stream ( 16 ) into the process stage c) to combine this stream ( 16 ) with the purified hydrogen chloride stream,
characterised in that
A) adjustable flow adjustment devices ( 50 , 51 , 52 , 53 ) are provided in the lines for the purified hydrogen chloride stream ( 3 ), the gas stream ( 11 ) remaining after chlorine separation, the partial gas stream ( 12 ) which is introduced into the waste gas treatment step and in the fresh oxygen-containing stream ( 15 ),
B) pressure measuring instruments ( 63 , 61 , 62 ) are provided downstream of or within the HCl gas purification step ( 31 ) for purification of the hydrogen chloride stream, in the chlorine separation ( 36 ) and in the line for the stream ( 11 ) remaining after the chlorine separation downstream of the flow adjustment device ( 51 ),
C) flow measuring instruments ( 71 , 72 , 73 ) are provided in the lines for the purified hydrogen chloride stream ( 3 ), the gas stream ( 13 ) remaining after the chlorine separation after discharging a partial stream ( 12 ) for waste gas treatment and the fresh oxygen-containing stream ( 15 ),
D) an instrument ( 81 ) for measuring the oxygen concentration is provided in the gas stream ( 13 ) remaining after the chlorine separation after discharging a partial stream ( 12 ) for waste gas treatment,
E) both the hydrogen chloride compression ( 30 ) and the chlorine compression ( 35 ) steps are provided with adjustable performance,
F) by means of a first control unit ( 91 ) the purified hydrogen chloride stream ( 3 ) is maintained at a constant rate of flow by adjusting the flow adjustment device ( 50 ) in this stream ( 3 ),
G) by means of a second control unit ( 92 ) the pressure measured in or downstream of the process step ( 31 ) for purifying the compressed hydrogen chloride stream is maintained at a constant value by adjusting the hydrogen chloride compression ( 30 ),
H) by means of a third control unit ( 93 ) the fresh oxygen-containing stream ( 15 ) is maintained at a constant flow rate ratio to the purified hydrogen chloride stream ( 3 ) by adjusting the flow adjustment device ( 53 ) in the fresh oxygen-containing stream ( 15 ),
I) by means of a fourth control unit ( 94 ) the aforementioned flow rate ratio between the fresh oxygen-containing stream ( 15 ) and the purified hydrogen chloride stream ( 3 ) is finely adjusted so that the oxygen content that is measured in the gas stream ( 13 ) remaining after the chlorine separation after discharge of a partial stream ( 12 ) for waste gas treatment is kept constant,
J) by means of a fifth control unit ( 95 ) the pressure measured in the gas stream ( 11 ) remaining after the chlorine separation ( 36 ) downstream of the flow adjustment device ( 51 ) is maintained at a constant value by adjusting the flow adjustment device ( 52 ) for the partial stream ( 12 ) introduced into the waste gas treatment ( 37 ),
K) by means of a sixth control device ( 96 ) the rate of flow of the gas stream ( 13 ) remaining after the chlorine separation after discharge of a partial stream ( 12 ) for waste gas treatment is maintained at a constant value by adjusting the chlorine compression step ( 35 ), and
L) by means of a seventh control device ( 97 ) the pressure measured in the chlorine separation ( 36 ) is maintained at a constant value by adjusting the flow adjustment device ( 51 ) in the gas stream ( 11 ) remaining after the chlorine separation ( 36 ).
2. The process according to claim 1 , characterised in that the oxygen concentration is measured in the gas stream ( 11 ) remaining after the chlorine separation, or in the partial stream ( 12 ) discharged to the waste gas treatment step, or in the stream ( 14 ) coming from the gas wash step ( 38 ), or in the stream ( 16 ) after combining the stream ( 14 ) with a fresh oxygen-containing stream ( 15 ).
3. The process according to claim 1 , characterised in that the pressure adjusted by the second control unit ( 92 ) is 2 to 20 bar,
the oxygen content adjusted by the fourth control unit ( 94 ) is 10 to 90 vol. %,
the pressure adjusted by the fifth control unit ( 95 ) is 2 to 20 bar,
and the pressure adjusted by the seventh control unit ( 97 ) is 6 to 30 bar.
4. The process according to claim 1 , characterised in that in the oxidation step ( 32 ) a ruthenium catalyst is used.
5. The process according to claim 1 , characterised in that in the oxidation step ( 32 ) a catalyst based on ruthenium chloride and tin oxide as carrier material is used.
6. A process for the production of chlorine by a catalysed gas phase oxidation of hydrogen chloride with an oxygen-containing gas stream, consisting of the process stages:
a) compressing a hydrogen chloride stream ( 1 ) in an HCl compression step ( 30 ) to an elevated pressure to obtain a compressed hydrogen chloride stream ( 2 );
b) purifying the compressed hydrogen chloride stream ( 2 ) in an HCl gas purification step ( 31 ) to obtain a purified hydrogen chloride stream ( 3 );
c) combining an oxygen-containing return stream ( 16 ) with the purified hydrogen chloride stream ( 3 ) to form a feedstock stream ( 4 );
d) introducing the feedstock stream ( 4 ) into an oxidation zone ( 32 ), in which hydrogen chloride and oxygen are partially reacted in the presence of a catalyst to form chlorine and water, and a product stream ( 5 ), containing chlorine, oxygen, hydrogen chloride and water, is obtained;
e) introducing the product stream ( 5 ) into a process step ( 33 ) for the separation of hydrogen chloride and water in the form of aqueous hydrochloric acid ( 6 ) from the product stream ( 5 ) to obtain a product stream ( 7 );
f) introducing the product stream ( 7 ) at least partly freed from hydrogen chloride and water into a drying step ( 34 ) for further drying with a reduction of the proportion of water in the product stream ( 7 );
g) introducing the dried gas stream ( 8 ) obtained from the drying step ( 34 ) into a chlorine compression step ( 35 ) to increase the pressure of the gas stream ( 8 ) with the formation of a compressed gas stream ( 9 );
h) introducing the compressed gas stream ( 9 ) into a separation step ( 36 ) for the at least partial separation of the chlorine ( 10 ) contained in the gas ( 9 ) with the formation of a gas stream ( 11 ), which contains unreacted oxygen;
i) combining at least a portion of gas stream ( 11 ) remaining after the chlorine separation ( 36 ), containing unreacted oxygen, with a stream ( 15 ) containing fresh oxygen to form an oxygen-containing return stream ( 16 );
j) a partial stream ( 12 ) of the gas stream ( 11 ) being discharged between the chlorine separation ( 36 ) and the forming of the oxygen containing return stream ( 16 );
k) introducing the discharged partial gas stream ( 12 ) into a waste gas treatment step ( 37 );
l) returning the return stream ( 16 ) into the process stage c) to combine this stream ( 16 ) with the purified hydrogen chloride stream,
characterised in that
A) adjustable flow adjustment devices ( 50 , 51 , 52 , 53 ) are provided in the lines for the purified hydrogen chloride stream ( 3 ), the gas stream ( 11 ) remaining after chlorine separation, the partial gas stream ( 12 ) which is introduced into the waste gas treatment step and in the fresh oxygen-containing stream ( 15 ),
B) pressure measuring instruments ( 63 , 61 , 62 ) are provided downstream of or within the HCl gas purification step ( 31 ) for purification of the hydrogen chloride stream, in the chlorine separation ( 36 ) and in the line for the stream ( 11 ) remaining after the chlorine separation downstream of the flow adjustment device ( 51 ),
C) flow measuring instruments ( 71 , 72 , 73 ) are provided in the lines for the purified hydrogen chloride stream ( 3 ), the gas stream ( 13 ) remaining after the chlorine separation after discharging a partial stream ( 12 ) for waste gas treatment and the fresh oxygen-containing stream ( 15 ),
D) an instrument ( 81 ) for measuring the oxygen concentration is provided in the gas stream ( 13 ) remaining after the chlorine separation after discharging a partial stream ( 12 ) for waste gas treatment,
E) both the hydrogen chloride compression ( 30 ) and the chlorine compression ( 35 ) steps are provided with adjustable performance,
F) by means of a first control unit ( 91 ) the purified hydrogen chloride stream ( 3 ) is maintained at a constant rate of flow by adjusting the flow adjustment device ( 50 ) in this stream ( 3 ),
G) by means of a second control unit ( 92 ) the pressure measured in or downstream of the process step ( 31 ) for purifying the compressed hydrogen chloride stream is maintained at a constant value by adjusting the hydrogen chloride compression ( 30 ),
H) by means of a third control unit ( 93 ) the fresh oxygen-containing stream ( 15 ) is maintained at a constant flow rate ratio to the purified hydrogen chloride stream ( 3 ) by adjusting the flow adjustment device ( 53 ) in the fresh oxygen-containing stream ( 15 ),
I) by means of a fourth control unit ( 94 ) the aforementioned flow rate ratio between the fresh oxygen-containing stream ( 15 ) and the purified hydrogen chloride stream ( 3 ) is finely adjusted so that the oxygen content that is measured in the gas stream ( 13 ) remaining after the chlorine separation after discharge of a partial stream ( 12 ) for waste gas treatment is kept constant,
J) by means of a fifth control unit ( 95 ) the pressure measured in the gas stream ( 11 ) remaining after the chlorine separation ( 36 ) downstream of the flow adjustment device ( 51 ) is maintained at a constant value by adjusting the flow adjustment device ( 52 ) for the partial stream ( 12 ) introduced into the waste gas treatment ( 37 ),
K) by means of a sixth control device ( 96 ) the rate of flow of the gas stream ( 13 ) remaining after the chlorine separation after discharge of a partial stream ( 12 ) for waste gas treatment is maintained at a constant value by adjusting the chlorine compression step ( 35 ), and
L) by means of a seventh control device ( 97 ) the pressure measured in the chlorine separation ( 36 ) is maintained at a constant value by adjusting the flow adjustment device ( 51 ) in the gas stream ( 11 ) remaining after the chlorine separation ( 36 ).
7. The process according to claim 6 , characterised in that the oxygen concentration is measured in the gas stream ( 11 ) remaining after the chlorine separation, or in the partial stream ( 12 ) discharged to the waste gas treatment step, or in the stream ( 16 ) after combining at least a portion of gas stream ( 11 ) with a fresh oxygen-containing stream ( 15 ).
8. The process according to claim 6 , characterised in that the pressure adjusted by the second control unit ( 92 ) is 2 to 20 bar,
the oxygen content adjusted by the fourth control unit ( 94 ) is 10 to 90 vol. %,
the pressure adjusted by the fifth control unit ( 95 ) is 2 to 20 bar,
and the pressure adjusted by the seventh control unit ( 97 ) is 6 to 30 bar.
9. The process according to claim 6 , characterised in that in the oxidation step ( 32 ) a ruthenium catalyst is used.
10. The process according to claim 6 , characterised in that in the oxidation step ( 32 ) a catalyst based on ruthenium chloride and tin oxide as carrier material is used.
11. A process for the production of chlorine by a catalysed gas phase oxidation of hydrogen chloride with an oxygen-containing gas stream, consisting of the process stages:
a) compressing a hydrogen chloride stream ( 1 ) in an HCl compression step ( 30 ) to an elevated pressure to obtain a compressed hydrogen chloride stream ( 2 );
b) purifying the compressed hydrogen chloride stream ( 2 ) in an HCl gas purification step ( 31 ) to obtain a purified hydrogen chloride stream ( 3 );
c) combining an oxygen-containing return stream ( 16 ) with the purified hydrogen chloride stream ( 3 ) to form a feedstock stream ( 4 );
d) introducing the feedstock stream ( 4 ) into an oxidation zone ( 32 ), in which hydrogen chloride and oxygen are partially reacted, in the presence of a catalyst, to form chlorine and water, and a product stream ( 5 ), containing chlorine, oxygen, hydrogen chloride and water, is obtained;
e) introducing the product stream ( 5 ) into a process step ( 33 ) for the separation of hydrogen chloride and water in the form of aqueous hydrochloric acid ( 6 ) from the product stream ( 5 ) to obtain a product stream ( 7 );
f) introducing the product stream ( 7 ) at least partly freed from hydrogen chloride and water into a drying step ( 34 ) for further drying with a reduction of the proportion of water in the product stream ( 7 );
g) introducing the dried gas stream ( 8 ) obtained from the drying step ( 34 ) into a chlorine compression step ( 35 ) to increase the pressure of the gas stream ( 8 ) with the formation of a compressed gas stream ( 9 );
h) introducing the compressed gas stream ( 9 ) into a separation step ( 36 ) for the at least partial separation of the chlorine ( 10 ) contained in the gas ( 9 ) with the formation of a gas stream ( 11 ), which contains unreacted oxygen;
i) introducing at least a portion of gas stream ( 11 ) remaining after the chlorine separation ( 36 ) into a gas-washing process step ( 38 ) to form a purified stream ( 14 ), a partial stream ( 12 ) of the gas stream ( 11 ) being discharged between the chlorine separation ( 36 ) and the gas-washing step ( 38 ) or downstream of the gas-washing step ( 38 );
j) introducing the discharged partial gas stream ( 12 ) into a waste gas treatment step ( 37 );
k) combining the stream ( 14 ) coming out of the gas-washing step ( 38 ), containing unreacted oxygen, with a stream ( 15 ) containing fresh oxygen to form an oxygen-containing return stream ( 16 );
l) returning the return stream ( 16 ) into the process stage c) to combine this stream ( 16 ) with the purified hydrogen chloride stream;
m) discharging a further partial stream ( 17 ) from the gas stream ( 11 ) remaining after the chlorine separation ( 36 ),
n) compressing the further partial stream ( 17 ) in a pressure increasing step ( 39 ) to obtain a compressed partial stream ( 18 ),
o) feeding the compressed partial stream ( 18 ) into a chlorine recovery step ( 40 ),
p) separating the chlorine contained in the compressed partial stream ( 18 ) by distillation at low temperature,
q) feeding the separated chlorine as a return stream ( 19 ) to the chlorine separation ( 36 ), and
r) feeding a gas stream ( 20 ) remaining after the chlorine has been separated in the chlorine recovery step ( 40 ) into the waste gas treatment ( 37 );
characterised in that
A) adjustable flow adjustment devices ( 50 , 51 , 52 , 53 ) are provided in the lines for the purified hydrogen chloride stream ( 3 ), the gas stream ( 11 ) remaining after chlorine separation, the partial gas stream ( 12 ) which is introduced into the waste gas treatment step and in the fresh oxygen-containing stream ( 15 ),
B) pressure measuring instruments ( 63 , 61 , 62 ) are provided downstream of or within the HCl gas purification step ( 31 ) for purification of the hydrogen chloride stream, in the chlorine separation ( 36 ) and in the line for the stream ( 11 ) remaining after the chlorine separation downstream of the flow adjustment device ( 51 ),
C) flow measuring instruments ( 71 , 72 , 73 ) are provided in the lines for the purified hydrogen chloride stream ( 3 ), the gas stream ( 13 ) remaining after the chlorine separation after discharging a partial stream ( 12 ) for waste gas treatment and the fresh oxygen-containing stream ( 15 ),
D) an instrument ( 81 ) for measuring the oxygen concentration is provided in the gas stream ( 13 ) remaining after the chlorine separation after discharging a partial stream ( 12 ) for waste gas treatment,
E) both the hydrogen chloride compression ( 30 ) and the chlorine compression ( 35 ) steps are provided with adjustable performance,
F) by means of a first control unit ( 91 ) the purified hydrogen chloride stream ( 3 ) is maintained at a constant rate of flow by adjusting the flow adjustment device ( 50 ) in this stream ( 3 ),
G) by means of a second control unit ( 92 ) the pressure measured in or downstream of the process step ( 31 ) for purifying the compressed hydrogen chloride stream is maintained at a constant value by adjusting the hydrogen chloride compression ( 30 ),
H) by means of a third control unit ( 93 ) the fresh oxygen-containing stream ( 15 ) is maintained at a constant flow rate ratio to the purified hydrogen chloride stream ( 3 ) by adjusting the flow adjustment device ( 53 ) in the fresh oxygen-containing stream ( 15 ),
I) by means of a fourth control unit ( 94 ) the aforementioned flow rate ratio between the fresh oxygen-containing stream ( 15 ) and the purified hydrogen chloride stream ( 3 ) is finely adjusted so that the oxygen content that is measured in the gas stream ( 13 ) remaining after the chlorine separation after discharge of a partial stream ( 12 ) for waste gas treatment is kept constant,
J) by means of a fifth control unit ( 95 ) the pressure measured in the gas stream ( 11 ) remaining after the chlorine separation ( 36 ) downstream of the flow adjustment device ( 51 ) is maintained at a constant value by adjusting the flow adjustment device ( 52 ) for the partial stream ( 12 ) introduced into the waste gas treatment ( 37 ),
K) by means of a sixth control device ( 96 ) the rate of flow of the gas stream ( 13 ) remaining after the chlorine separation after discharge of a partial stream ( 12 ) for waste gas treatment is maintained at a constant value by adjusting the chlorine compression step ( 35 ), and
L) by means of a seventh control device ( 97 ) the pressure measured in the chlorine separation ( 36 ) is maintained at a constant value by adjusting the flow adjustment device ( 51 ) in the gas stream ( 11 ) remaining after the chlorine separation ( 36 );
M) an adjustable flow adjustment device ( 54 ) is provided in the line of the gas stream ( 20 ) remaining after the chlorine recovery step ( 40 );
N) a flow measuring instrument ( 74 ) is provided in the further partial stream ( 17 ), which is passed into the pressure increasing step ( 39 );
O) a pressure measuring instrument ( 64 ) is provided in or downstream of the chlorine recovery step ( 40 ), upstream of the flow adjustment device ( 54 ) for the gas stream ( 20 ) remaining after this step;
P) the pressure increasing device ( 39 ) is provided with adjustable performance;
Q) by means of an eighth control device ( 98 ) the flow rate of the further partial stream ( 17 ) is adjusted by adjusting the performance of the pressure increasing device ( 39 ) such that the partial stream ( 12 ) to the waste gas treatment ( 37 ) described above is minimised, and
R) by means of a ninth control device ( 99 ) the pressure measured in or downstream of the chlorine recovery step ( 40 ) is kept constant by adjusting the flow adjustment device 54 .
12. The process according to claim 11 , characterised in that
the oxygen concentration is measured in the gas stream ( 11 ) remaining after the chlorine separation, or in the partial stream ( 12 ) discharged to the waste gas treatment step, or in the stream ( 16 ) after combining at least a portion of gas stream ( 11 ) with a fresh oxygen-containing stream ( 15 ).
13. The process according to claim 11 , characterised in that the pressure adjusted by the second control unit ( 92 ) is 2 to 20 bar,
the oxygen content adjusted by the fourth control unit ( 94 ) is 10 to 90 vol. %,
the pressure adjusted by the fifth control unit ( 95 ) is 2 to 20 bar,
and the pressure adjusted by the seventh control unit ( 97 ) is 6 to 30 bar.
14. The process according to claim 11 , characterised in that in the oxidation step ( 32 ) a ruthenium catalyst is used.
15. The process according to claim 11 , characterised in that in the oxidation step ( 32 ) a catalyst based on ruthenium chloride and tin oxide as carrier material is used.
16. The process according to claim 11 , characterised in that
the oxygen concentration is measured in the gas stream ( 11 ) remaining after the chlorine separation, or in the partial stream ( 12 ) discharged to the waste gas treatment step, or in the further partial stream ( 17 ) discharged to the pressure increasing step, or in the stream ( 14 ) coming from the gas wash step ( 38 ), or in the stream ( 16 ) after combining the stream ( 14 ) with a fresh oxygen-containing stream ( 15 ).