CA2054031A1 - A method for producing hydrochloric acid - Google Patents
A method for producing hydrochloric acidInfo
- Publication number
- CA2054031A1 CA2054031A1 CA 2054031 CA2054031A CA2054031A1 CA 2054031 A1 CA2054031 A1 CA 2054031A1 CA 2054031 CA2054031 CA 2054031 CA 2054031 A CA2054031 A CA 2054031A CA 2054031 A1 CA2054031 A1 CA 2054031A1
- Authority
- CA
- Canada
- Prior art keywords
- methanol
- reaction
- hydrochloric acid
- chlorine
- amount
- 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.)
- Abandoned
Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 150
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims abstract description 36
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000460 chlorine Substances 0.000 claims abstract description 31
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 31
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 18
- 235000019398 chlorine dioxide Nutrition 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960000443 hydrochloric acid Drugs 0.000 claims description 45
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 13
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 description 29
- 239000002253 acid Substances 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YWIULWOWYIZJBX-UHFFFAOYSA-N [Cl].O1C=COC=C1 Chemical compound [Cl].O1C=COC=C1 YWIULWOWYIZJBX-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the disclosure The present invention relates to a method for producing hydrochloric acid or a solution of hydrochloric acid and methanol by reacting chlorine with methanol in the presence of water at an elevated temperature and by allowing light to affect the reaction solution in a reaction tower. The invention also relates to the usage of a reaction solution containing hydrochloric acid and methanol achieved by this method for producing chlorine dioxide from sodium chlorate and hydrochloric acid in the presence of a reducing agent.
Description
XC5~33:1.
A method for producing hydrochloric acid The present invention relates to a method for producing hydrochloric acid of chlorine and methanol according to the following reaction:
CH30H+3C12IH20 = 6HCltC02 In addition the invention reiates to the application of hydrochloric acid or a mixture of hydrochloric acid and methanol achieved in this way in the production of chlorine dioxide.
The above mentioned reaction is known per se, especially in order to eliminate the chlorine produced as a reaction by-product in connection with the production of chlorine dloxide, from Finnish Patent Applications Nos. 895028, 894901 and 881440. In the method the by-product of the preparation of chlorine dioxine, i.e. chlorine reacts with a reducing agent, for example, methanol. This process is, however, not used in order to produce hydrochloric acid.
Now it has been surprisingly discovered in connection with the present invention that the yield of the reaction is considerably improved by light. Thus the object of the invention is an improvement in the performance of a reaction known per se.
Presently hydrochloric acid is produced by reacting chlorine gas and hydrogen gas in a hydrochloric acid burner of special construction specially planned for this.
Since the amount of hydrogen necessarily needed in the process is high, and it is not practical to transport in large amounts, the production of hydrochloric acid is in practice possible only in the close vicinity of a large hydrogen source, for example, a chlorine or chlorate 2 zc~
plant. This again raises the transport costs of hydro-chloric acid, whose normal commercial grade is a 32 per cent aqueous solution, because more than two thirds of the load consists of water. The present invention enables production of hydrochloric acid on a large scale at the location where the hydrochloric acid is used without the need of hydrogen gas or specially built burners able to endure high temperatures.
The invention is especially well suited for the production of chlorine dioxide.
Due to reasons of environment protection the aim is nowadays to avoid such methods of producing hydrochloric acid in which sulphur compounds are used. In such cases it would be practical to use methods based on hydrochloric acid already available on the mar~et, for example, the R5-method o ERC0, in which chlorine dioxide is produced of sodium chlorate and hydrochloric acid. There are, however, two complications involved in the application of these:
1. The extent of the amount hydrochloric acid needed. A
reactor producing 30 tons of chlorine dioxide during 24 hours uses about 40 tons of 100 per cent hydrochloric acid, i.e. more than 120 tons of 32 per cent solution in 24 hours.
2. The chlorine formed as a by-product. Because of environmental control reasons the tendency nowadays is to decrease the use of chlorine in bleaching, and the above mentioned reactor producing 30 tons of chlorine dioxide produces as a by-product 20 tons of chlorine.
With the method for producing hydrochlorite acid according to the present invention both above disclosed problems can be solved. When producing 40 tons of 100 per cent hydro-chloric acid only about 40 tons of chlorine and 6 tons of - 3 - ~ 31.
methanolare needed in theory. The chlorine achieved as a by-product may be utilized here, thus only 20 tons of fresh chlorine is needed in theory.
By the method according to the invention hydro-chloric acid is produced so that the chlorine is reacted with the aqueous solution of methanol at an elevated temperature and then light is allowed to affect the reaction mixture. The water dilutes the reaction mixture, assists in the heat transmission and hydrolyzes possible intermediate products.
According to one aspect of the present invention there is provided a process for preparing hydrogen chloride which comprises reacting chlorine and methanol in contact with water at an elevated temperature and while exposing the reaction mix-ture to light.
In some preferred embodiments the process comprises:
further reaction of the hydrogen chloride with sodium chlorate in contact with a reducing agent to obtain chlorine dioxide; the reaction to obtain hydrogen chloride is effected in a reaction tower and the reducing agent in the preparation of the chlorine dioxide is a mixture of hydrogen chloride and methanol vapour leaving the reaction tower; the hydrogen chloride and reducing agent comprises a mixture of hydrogen chloride, methanol and water.
Figure 1 shows a schematic view of an apparatus with which the reaction can be carried out. A mixture of methanol and water is circulated in the apparatus and the chlorine is fed into the gas space of the tower. In the following said device XC~3~
- 3a - 66600-183 will be called the reaction tower and the solution circulating in lt the reaction solution.
At a normal air pressure the HCl content of the reaction solution rises to a level of 30 to 35 per cent, after which the formed hydrochloric acid leaves the reaction tower.
With the aim of recovery of the hydrochloric acid, an absorption tower is mounted after the reaction tower with an absorption solution circulating in it.
The apparatus may be used either batchwise or con-tinuously. In the batchwise use the reaction solution circula-tion is charged with a sufficient amount of methanol and chlorine is continuously fed. The hydrochloric acid content of the reaction solution increases and the methanol content decreases.
When the hydrochloric acid content reaches a level of 30 to 35 per cent, the acid starts to exit from the reaction tower in a ZC5~31 gaC;eous form, whereby the concentration of the absorption solution starts to increase. When the apparatus is used continuously the reaction tower is continuously fed with a mixture of methanol and water, simultaneously acid may be removed from the tower continuously.
With regard to the further use of hydrochloric acid it is important that it is produced as concentrated as possible.
Hereby the reaction is carried out so that the reaction solution is allowed to become so concentrated with respect to the hydrochloric acid that the hydrochloric acid starts to exit from the reaction tower to the absorption tower.
Since the methanol contained in the reaction solution contains steam pressure, also methanol exits with the hydrochloric acid and is absorbed into the water circulating in the absorption tower. Hereby a solution is received out from the absorption tower containing both hydrochloric acid and methanol. The methanol content is not disadvantageous if the hydrochloric acid is used for producing chlorine dioxide.
In the method according to U.S. Patent No. 4,081,520 for producing chlorine dioxide using sodium chlorate as reactant, methanol is used as reducing agent in a sulphur acidic solution. In the method according to the invention chlorine dioxide is produced from sodium chlorate and hydrochloric acid in the presence of a reducing agent. As the hydrochloric acid and reducing agent needed in the reaction the solution containing hydrochloric acid and methanol according to the method of Figure l is uded.
When producing chlorine dioxide it is possible to use hydrochloric acid produced by the method according to the invention, a reaction solution circulating in the reaction tower (exit point A, Figure 1) containing in addition to the acid methanol used as reducing agent, or a gaseous mixture of hydrochloric acid and methanol exiting from the ~C5~
reaction tower (exit point B, Figure 1), which can be absorbed into a suitable flow circulating in the chlorine dioxide reactor. Hereby it is possible to raise the acid concentration in the chlorine dioxide reactor, which is advantageous with respect to the reaction. Naturally, it is possible to use the hydrochloric acid solution exiting from the absorption tower (exit point C, Figure 1) as the acid being fed into the chlorine dioxide reactor.
By experiment it has been stated that in a totally closed device the reaction between chlorine and methanol begins with a relatively good yield when fresh solvents are being used, i.e. when the reaction solution does not yet contain hydrochloric acid in large amounts. When the hydrochloric acid content rises to the vicinity of 20%, the efficiency falls. According to the invention it has surprisingly been found that when light is allowed to affect the reaction mixture the yield increases notably and hydrochloric acid contents reaching 30% are easily achieved in the reaction mixture.
The invention will be more closely illustrated with the help of the following example.
Exam~les Six tests were carried out, the four first were not exposed to light, and in the tests five and six light was allowed to affect the reaction mixture during the reaction. In all tests the temperature was 60 to 70C, often 63 to 68C. In the course of the test the reaction temperature usually raised the temperature about 5 degrees during 7 hours. The test results are presented in the following tables.
6 X~ 31 Example 1.
Reaction solution Hydrochloric Methanol acid 5vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 36.00 0.992 35.71 3.55 1.27 12.70 4.54 end 37.00 1.038 38.41 12.50 4.80 10.10 3.88 change 3.53 -0.66 Absorption Hydrochloric Methanol solution acid vol/l spec. amount/ % amount/ % amount/
15weight kg kg kg beginning 13.10 0.998 13.07 0.50 0.07 0.98 0.13 end 13.40 1.003 13~44 1.60 0.22 1.52 0.20 change 0.15 0.08 Feed of chlorine/kg 3.80 HCl-yield/kg 3.68 Theoretical yield/% 94.23 kg Methanol consumption 0.58 Theoretical consumption/HCl-yield 0.54 92.95 Theoretical consumption/Cl-feed 0.57 98.65 Example 2.
Reaction solution Hydrochloric Methanol acid vol/l spec. amount/ % amount/ % amount/
35weight kg kg kg beginning 37.00 1.042 38.55 12.70 4.90 9.48 3.65 end 37.00 1.053 38.96 15.20 5.92 7.86 3.06 change 1.03 -0.59 7 ~C~ 331 Absorption Hydrochloric Methanol solution acid vol/1 spec. amount/ % amount/ % amount/
weight kg kg kg beginning 13.70 1.005 13.77 1.84 0.25 1.83 0.25 end 13.70 1.010 13.84 3.24 0.452.40 0.33 change 0.19 0.08 Feed of chlorine/kg 2.00 HCl-yield/kg 1.22 Theoretical yield/% 59.34 kg %
Methanol consumption 0.51 Theoretical consumption/HCl-yield 0.18 34.89 Theoretical consumption/Cl-feed 0.30 58.79 Example 3.
Reaction solution Hydrochloric Methanol acid vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 36.00 1.050 37.80 15.00 5.67 11.30 4.27 end 36.00 1.064 38.30 17.80 6.82 9.02 3.46 change 1.15 -0.82 Absorption Hydrochloric Methanol solution acid vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 13.00 1.010 13.13 3.24 0.43 2.40 0.32 end 13.00 1.021 13.27 5.78 0.77 3.71 0.49 change 0.34 0.18 Feed of chlorine/kg 3.00 HCl-yield/kg 1.49 Theoretical yield/% 48.29 XC~831.
kg Methanol consumption 0.64 Theoretical consumption/HCl-yield 0.22 34.14 Theoretical consumption/Cl-feed 0.45 70.71 Example 4.
Reaction solution Hydrochloric Methanol acid vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 36.00 1.054 37.94 16.80 6.37 10.80 4.10 end 36.00 1.058 38.09 17.90 6.82 10.40 3.96 change 0.44 -0,14 Absorption Hydrochloric Methanol solution acid vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 13.00 1.021 13.27 5.78 0.77 3.71 0.49 end 13.00 1.026 13.34 6.85 0.91 4.30 0.57 change 0.15 0.08 Feed of chlorine/kg 1.20 HCl-yield/kg 0.59 Theoretical yield/% 47.77 kg %
Methanol consumption 0.06 Theoretical consumption/HCl-yield0.09 155.06 Theoretical consumption/Cl-feed 0.18 324.56 9 2C5 ~3~
Example 5.
Reaction solution Hydrochloric Methanol acid 5vol/l spec. amount/ ~ amount/ ~ amount/
weight kg kg kg beginning 36.00 1.059 38.12 17.60 6.71 11.80 4.50 end 37.00 1.096 40.55 23.40 9.49 8.48 3.44 change 2.78 -1.06 Absorption Hydrochloric Methanol solution acid vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 13.00 1.033 13.43 9.10 1.22 6.46 0.87 end 13.40 1.033 13.84 9.34 1.29 6.37 0.88 change 0.07 0.01 Feed of chlorine/kg 3.60 HCl-yleld/kg 2.85 Theoretical yield/% 76.98 kg %
Methanol consumption 1.05 Theoretical consumption/HCl-yield 0.42 39.92 Theoretical consumption/Cl-feed 0.54 51.86 In this test light was allowed to affect the reaction solution during the reaction.
Example 6.
Reaction solution Hydrochloric Methanol acid vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 37.00 l.090 40.33 22.70 9.15 8.40 3.39 end 37.00 1.133 41.92 29.10 12.20 5.44 2.28 change 3.04 -1.11 ~C~31 Absorption Hydrochloric Methanol solution acid vol/l spec. amount/ % amount/ % amount/
weight kg kg ~g beginning 13.40 1.033 13.84 9.341.29 6.37 0.88 end 13.50 1.04114.05 11.10 1.567.90 1.11 change 0.27 0.23 Feed of chlorine/kg 4.20 HC1-yield/kg 3.31 Theoretical yield/% 76.65 kg %
Methanol consumption 0.88 Theoretical consumption/HCl-yield 0.48 55.19 Theoretical consumption/Cl-feed 0.63 72.00 In this test light was allowed to affect the reaction solution during the reaction.
In tests 1 to 4 it was observed that chlorine passes through the absorption system according to Figure 1 partly without reacting. In tests 5 and 6 no passing through was observed.
The feeding rate of chlorine varied between 7.5 and 10 gr per minute. In all tests the device was at the beginning of the test nitrified and at the end of the test there was a certain amount of unreacted chlorine in the gas space of the device. It was not possible to observe the unreacted chlorine in the material balance. thus the yield percentage of hydrochloric acid calculated on the basis of the input amount of chlorine is sligtly too small. The reaction catalyzing effect of light can be clearly seen as a jump in the yield percentage when comparing tests 1 to 4 with tests 5 and 6.
A method for producing hydrochloric acid The present invention relates to a method for producing hydrochloric acid of chlorine and methanol according to the following reaction:
CH30H+3C12IH20 = 6HCltC02 In addition the invention reiates to the application of hydrochloric acid or a mixture of hydrochloric acid and methanol achieved in this way in the production of chlorine dioxide.
The above mentioned reaction is known per se, especially in order to eliminate the chlorine produced as a reaction by-product in connection with the production of chlorine dloxide, from Finnish Patent Applications Nos. 895028, 894901 and 881440. In the method the by-product of the preparation of chlorine dioxine, i.e. chlorine reacts with a reducing agent, for example, methanol. This process is, however, not used in order to produce hydrochloric acid.
Now it has been surprisingly discovered in connection with the present invention that the yield of the reaction is considerably improved by light. Thus the object of the invention is an improvement in the performance of a reaction known per se.
Presently hydrochloric acid is produced by reacting chlorine gas and hydrogen gas in a hydrochloric acid burner of special construction specially planned for this.
Since the amount of hydrogen necessarily needed in the process is high, and it is not practical to transport in large amounts, the production of hydrochloric acid is in practice possible only in the close vicinity of a large hydrogen source, for example, a chlorine or chlorate 2 zc~
plant. This again raises the transport costs of hydro-chloric acid, whose normal commercial grade is a 32 per cent aqueous solution, because more than two thirds of the load consists of water. The present invention enables production of hydrochloric acid on a large scale at the location where the hydrochloric acid is used without the need of hydrogen gas or specially built burners able to endure high temperatures.
The invention is especially well suited for the production of chlorine dioxide.
Due to reasons of environment protection the aim is nowadays to avoid such methods of producing hydrochloric acid in which sulphur compounds are used. In such cases it would be practical to use methods based on hydrochloric acid already available on the mar~et, for example, the R5-method o ERC0, in which chlorine dioxide is produced of sodium chlorate and hydrochloric acid. There are, however, two complications involved in the application of these:
1. The extent of the amount hydrochloric acid needed. A
reactor producing 30 tons of chlorine dioxide during 24 hours uses about 40 tons of 100 per cent hydrochloric acid, i.e. more than 120 tons of 32 per cent solution in 24 hours.
2. The chlorine formed as a by-product. Because of environmental control reasons the tendency nowadays is to decrease the use of chlorine in bleaching, and the above mentioned reactor producing 30 tons of chlorine dioxide produces as a by-product 20 tons of chlorine.
With the method for producing hydrochlorite acid according to the present invention both above disclosed problems can be solved. When producing 40 tons of 100 per cent hydro-chloric acid only about 40 tons of chlorine and 6 tons of - 3 - ~ 31.
methanolare needed in theory. The chlorine achieved as a by-product may be utilized here, thus only 20 tons of fresh chlorine is needed in theory.
By the method according to the invention hydro-chloric acid is produced so that the chlorine is reacted with the aqueous solution of methanol at an elevated temperature and then light is allowed to affect the reaction mixture. The water dilutes the reaction mixture, assists in the heat transmission and hydrolyzes possible intermediate products.
According to one aspect of the present invention there is provided a process for preparing hydrogen chloride which comprises reacting chlorine and methanol in contact with water at an elevated temperature and while exposing the reaction mix-ture to light.
In some preferred embodiments the process comprises:
further reaction of the hydrogen chloride with sodium chlorate in contact with a reducing agent to obtain chlorine dioxide; the reaction to obtain hydrogen chloride is effected in a reaction tower and the reducing agent in the preparation of the chlorine dioxide is a mixture of hydrogen chloride and methanol vapour leaving the reaction tower; the hydrogen chloride and reducing agent comprises a mixture of hydrogen chloride, methanol and water.
Figure 1 shows a schematic view of an apparatus with which the reaction can be carried out. A mixture of methanol and water is circulated in the apparatus and the chlorine is fed into the gas space of the tower. In the following said device XC~3~
- 3a - 66600-183 will be called the reaction tower and the solution circulating in lt the reaction solution.
At a normal air pressure the HCl content of the reaction solution rises to a level of 30 to 35 per cent, after which the formed hydrochloric acid leaves the reaction tower.
With the aim of recovery of the hydrochloric acid, an absorption tower is mounted after the reaction tower with an absorption solution circulating in it.
The apparatus may be used either batchwise or con-tinuously. In the batchwise use the reaction solution circula-tion is charged with a sufficient amount of methanol and chlorine is continuously fed. The hydrochloric acid content of the reaction solution increases and the methanol content decreases.
When the hydrochloric acid content reaches a level of 30 to 35 per cent, the acid starts to exit from the reaction tower in a ZC5~31 gaC;eous form, whereby the concentration of the absorption solution starts to increase. When the apparatus is used continuously the reaction tower is continuously fed with a mixture of methanol and water, simultaneously acid may be removed from the tower continuously.
With regard to the further use of hydrochloric acid it is important that it is produced as concentrated as possible.
Hereby the reaction is carried out so that the reaction solution is allowed to become so concentrated with respect to the hydrochloric acid that the hydrochloric acid starts to exit from the reaction tower to the absorption tower.
Since the methanol contained in the reaction solution contains steam pressure, also methanol exits with the hydrochloric acid and is absorbed into the water circulating in the absorption tower. Hereby a solution is received out from the absorption tower containing both hydrochloric acid and methanol. The methanol content is not disadvantageous if the hydrochloric acid is used for producing chlorine dioxide.
In the method according to U.S. Patent No. 4,081,520 for producing chlorine dioxide using sodium chlorate as reactant, methanol is used as reducing agent in a sulphur acidic solution. In the method according to the invention chlorine dioxide is produced from sodium chlorate and hydrochloric acid in the presence of a reducing agent. As the hydrochloric acid and reducing agent needed in the reaction the solution containing hydrochloric acid and methanol according to the method of Figure l is uded.
When producing chlorine dioxide it is possible to use hydrochloric acid produced by the method according to the invention, a reaction solution circulating in the reaction tower (exit point A, Figure 1) containing in addition to the acid methanol used as reducing agent, or a gaseous mixture of hydrochloric acid and methanol exiting from the ~C5~
reaction tower (exit point B, Figure 1), which can be absorbed into a suitable flow circulating in the chlorine dioxide reactor. Hereby it is possible to raise the acid concentration in the chlorine dioxide reactor, which is advantageous with respect to the reaction. Naturally, it is possible to use the hydrochloric acid solution exiting from the absorption tower (exit point C, Figure 1) as the acid being fed into the chlorine dioxide reactor.
By experiment it has been stated that in a totally closed device the reaction between chlorine and methanol begins with a relatively good yield when fresh solvents are being used, i.e. when the reaction solution does not yet contain hydrochloric acid in large amounts. When the hydrochloric acid content rises to the vicinity of 20%, the efficiency falls. According to the invention it has surprisingly been found that when light is allowed to affect the reaction mixture the yield increases notably and hydrochloric acid contents reaching 30% are easily achieved in the reaction mixture.
The invention will be more closely illustrated with the help of the following example.
Exam~les Six tests were carried out, the four first were not exposed to light, and in the tests five and six light was allowed to affect the reaction mixture during the reaction. In all tests the temperature was 60 to 70C, often 63 to 68C. In the course of the test the reaction temperature usually raised the temperature about 5 degrees during 7 hours. The test results are presented in the following tables.
6 X~ 31 Example 1.
Reaction solution Hydrochloric Methanol acid 5vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 36.00 0.992 35.71 3.55 1.27 12.70 4.54 end 37.00 1.038 38.41 12.50 4.80 10.10 3.88 change 3.53 -0.66 Absorption Hydrochloric Methanol solution acid vol/l spec. amount/ % amount/ % amount/
15weight kg kg kg beginning 13.10 0.998 13.07 0.50 0.07 0.98 0.13 end 13.40 1.003 13~44 1.60 0.22 1.52 0.20 change 0.15 0.08 Feed of chlorine/kg 3.80 HCl-yield/kg 3.68 Theoretical yield/% 94.23 kg Methanol consumption 0.58 Theoretical consumption/HCl-yield 0.54 92.95 Theoretical consumption/Cl-feed 0.57 98.65 Example 2.
Reaction solution Hydrochloric Methanol acid vol/l spec. amount/ % amount/ % amount/
35weight kg kg kg beginning 37.00 1.042 38.55 12.70 4.90 9.48 3.65 end 37.00 1.053 38.96 15.20 5.92 7.86 3.06 change 1.03 -0.59 7 ~C~ 331 Absorption Hydrochloric Methanol solution acid vol/1 spec. amount/ % amount/ % amount/
weight kg kg kg beginning 13.70 1.005 13.77 1.84 0.25 1.83 0.25 end 13.70 1.010 13.84 3.24 0.452.40 0.33 change 0.19 0.08 Feed of chlorine/kg 2.00 HCl-yield/kg 1.22 Theoretical yield/% 59.34 kg %
Methanol consumption 0.51 Theoretical consumption/HCl-yield 0.18 34.89 Theoretical consumption/Cl-feed 0.30 58.79 Example 3.
Reaction solution Hydrochloric Methanol acid vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 36.00 1.050 37.80 15.00 5.67 11.30 4.27 end 36.00 1.064 38.30 17.80 6.82 9.02 3.46 change 1.15 -0.82 Absorption Hydrochloric Methanol solution acid vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 13.00 1.010 13.13 3.24 0.43 2.40 0.32 end 13.00 1.021 13.27 5.78 0.77 3.71 0.49 change 0.34 0.18 Feed of chlorine/kg 3.00 HCl-yield/kg 1.49 Theoretical yield/% 48.29 XC~831.
kg Methanol consumption 0.64 Theoretical consumption/HCl-yield 0.22 34.14 Theoretical consumption/Cl-feed 0.45 70.71 Example 4.
Reaction solution Hydrochloric Methanol acid vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 36.00 1.054 37.94 16.80 6.37 10.80 4.10 end 36.00 1.058 38.09 17.90 6.82 10.40 3.96 change 0.44 -0,14 Absorption Hydrochloric Methanol solution acid vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 13.00 1.021 13.27 5.78 0.77 3.71 0.49 end 13.00 1.026 13.34 6.85 0.91 4.30 0.57 change 0.15 0.08 Feed of chlorine/kg 1.20 HCl-yield/kg 0.59 Theoretical yield/% 47.77 kg %
Methanol consumption 0.06 Theoretical consumption/HCl-yield0.09 155.06 Theoretical consumption/Cl-feed 0.18 324.56 9 2C5 ~3~
Example 5.
Reaction solution Hydrochloric Methanol acid 5vol/l spec. amount/ ~ amount/ ~ amount/
weight kg kg kg beginning 36.00 1.059 38.12 17.60 6.71 11.80 4.50 end 37.00 1.096 40.55 23.40 9.49 8.48 3.44 change 2.78 -1.06 Absorption Hydrochloric Methanol solution acid vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 13.00 1.033 13.43 9.10 1.22 6.46 0.87 end 13.40 1.033 13.84 9.34 1.29 6.37 0.88 change 0.07 0.01 Feed of chlorine/kg 3.60 HCl-yleld/kg 2.85 Theoretical yield/% 76.98 kg %
Methanol consumption 1.05 Theoretical consumption/HCl-yield 0.42 39.92 Theoretical consumption/Cl-feed 0.54 51.86 In this test light was allowed to affect the reaction solution during the reaction.
Example 6.
Reaction solution Hydrochloric Methanol acid vol/l spec. amount/ % amount/ % amount/
weight kg kg kg beginning 37.00 l.090 40.33 22.70 9.15 8.40 3.39 end 37.00 1.133 41.92 29.10 12.20 5.44 2.28 change 3.04 -1.11 ~C~31 Absorption Hydrochloric Methanol solution acid vol/l spec. amount/ % amount/ % amount/
weight kg kg ~g beginning 13.40 1.033 13.84 9.341.29 6.37 0.88 end 13.50 1.04114.05 11.10 1.567.90 1.11 change 0.27 0.23 Feed of chlorine/kg 4.20 HC1-yield/kg 3.31 Theoretical yield/% 76.65 kg %
Methanol consumption 0.88 Theoretical consumption/HCl-yield 0.48 55.19 Theoretical consumption/Cl-feed 0.63 72.00 In this test light was allowed to affect the reaction solution during the reaction.
In tests 1 to 4 it was observed that chlorine passes through the absorption system according to Figure 1 partly without reacting. In tests 5 and 6 no passing through was observed.
The feeding rate of chlorine varied between 7.5 and 10 gr per minute. In all tests the device was at the beginning of the test nitrified and at the end of the test there was a certain amount of unreacted chlorine in the gas space of the device. It was not possible to observe the unreacted chlorine in the material balance. thus the yield percentage of hydrochloric acid calculated on the basis of the input amount of chlorine is sligtly too small. The reaction catalyzing effect of light can be clearly seen as a jump in the yield percentage when comparing tests 1 to 4 with tests 5 and 6.
Claims (8)
1. A process for preparing hydrogen chloride which comprises reacting chlorine and methanol in contact with water at an elevated temperature and while exposing the reaction mix-ture to light.
2. A process according to claim 1 comprising further reaction of the hydrogen chloride with sodium chlorate in contact with a reducing agent to obtain chlorine dioxide.
3. A process according to claim 2 wherein the reaction to obtain hydrogen chloride is effected in a reaction tower and the reducing agent in the preparation of the chlorine dioxide is a mixture of hydrogen chloride and methanol vapour leaving the reaction tower.
4. A process according to claim 2 wherein the hydrogen chloride and reducing agent comprises a mixture of hydrogen chloride, methanol and water.
5. A method for producing hydrochloric acid or a solution of hydrochloric acid and methanol by reacting chlorine with methanol in the presence of water, characterized in that the reaction is implemented at an elevated temperature and light is allowed to affect the reaction solution in a reaction tower.
6. Usage of such a reaction solution containing hydro-chloric acid and methanol for producing chlorine dioxide from sodium chlorate in the presence of a reducing agent, which solution is produced by reacting chlorine with methanol in the presence of water at an elevated temperature and by allowing light to affect the reaction solution.
7. Usage according to claim 6, characterized in that the hydrochloric acid and reducing agent used in the reaction is the mixture of hydrochloric acid and methanol vapour exiting from the reaction tower.
8. Usage according to claim 6, characterized in that the hydrochloric acid and reducing agent used in the reaction is a mixture of hydrochloric acid and methanol and water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI905245A FI85007C (en) | 1990-10-24 | 1990-10-24 | Process for the production of hydrochloric acid |
| FI905245 | 1990-10-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2054031A1 true CA2054031A1 (en) | 1992-04-25 |
Family
ID=8531302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2054031 Abandoned CA2054031A1 (en) | 1990-10-24 | 1991-10-23 | A method for producing hydrochloric acid |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPH04265202A (en) |
| AT (1) | AT404127B (en) |
| BR (1) | BR9104587A (en) |
| CA (1) | CA2054031A1 (en) |
| FI (1) | FI85007C (en) |
| FR (1) | FR2668463B1 (en) |
| PT (1) | PT99314B (en) |
| SE (1) | SE9103032L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038459A (en) * | 2019-05-22 | 2019-07-23 | 蚌埠学院 | A kind of device and preparation method thereof preparing hydrogen chloride methanol solution |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3351505A1 (en) * | 2017-01-20 | 2018-07-25 | Covestro Deutschland AG | Method for flexible control of the use of hydrochloric acid from chemical production |
-
1990
- 1990-10-24 FI FI905245A patent/FI85007C/en not_active IP Right Cessation
-
1991
- 1991-10-18 SE SE9103032A patent/SE9103032L/en not_active Application Discontinuation
- 1991-10-22 AT AT210791A patent/AT404127B/en not_active IP Right Cessation
- 1991-10-23 FR FR9113093A patent/FR2668463B1/en not_active Expired - Fee Related
- 1991-10-23 JP JP30402191A patent/JPH04265202A/en active Pending
- 1991-10-23 BR BR9104587A patent/BR9104587A/en unknown
- 1991-10-23 PT PT9931491A patent/PT99314B/en not_active IP Right Cessation
- 1991-10-23 CA CA 2054031 patent/CA2054031A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038459A (en) * | 2019-05-22 | 2019-07-23 | 蚌埠学院 | A kind of device and preparation method thereof preparing hydrogen chloride methanol solution |
| CN110038459B (en) * | 2019-05-22 | 2024-01-19 | 蚌埠学院 | Device for preparing hydrogen chloride methanol solution and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| FI85007C (en) | 1992-02-25 |
| ATA210791A (en) | 1998-01-15 |
| SE9103032D0 (en) | 1991-10-18 |
| FR2668463B1 (en) | 1993-10-15 |
| JPH04265202A (en) | 1992-09-21 |
| SE9103032L (en) | 1992-04-25 |
| BR9104587A (en) | 1992-06-09 |
| FI905245A (en) | 1991-11-15 |
| PT99314A (en) | 1992-09-30 |
| AT404127B (en) | 1998-08-25 |
| FI905245A0 (en) | 1990-10-24 |
| FR2668463A1 (en) | 1992-04-30 |
| FI85007B (en) | 1991-11-15 |
| PT99314B (en) | 1999-04-30 |
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