CA2054031A1 - A method for producing hydrochloric acid - Google Patents

A method for producing hydrochloric acid

Info

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
Application number
CA 2054031
Other languages
French (fr)
Inventor
Reijo Seppanen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nokia AB Chemicals Oy
Original Assignee
Reijo Seppanen
Oy Nokia Ab Chemicals
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Reijo Seppanen, Oy Nokia Ab Chemicals filed Critical Reijo Seppanen
Publication of CA2054031A1 publication Critical patent/CA2054031A1/en
Abandoned legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/01Chlorine; Hydrogen chloride
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02Oxides of chlorine
    • C01B11/022Chlorine dioxide (ClO2)
    • C01B11/023Preparation from chlorites or chlorates

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  • 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.

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.
CA 2054031 1990-10-24 1991-10-23 A method for producing hydrochloric acid Abandoned CA2054031A1 (en)

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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Cited By (2)

* Cited by examiner, † Cited by third party
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
JPH04265202A (en) 1992-09-21
FI85007B (en) 1991-11-15
FI905245A0 (en) 1990-10-24
FR2668463B1 (en) 1993-10-15
AT404127B (en) 1998-08-25
SE9103032L (en) 1992-04-25
FI85007C (en) 1992-02-25
FR2668463A1 (en) 1992-04-30
BR9104587A (en) 1992-06-09
FI905245A (en) 1991-11-15
PT99314A (en) 1992-09-30
ATA210791A (en) 1998-01-15
SE9103032D0 (en) 1991-10-18
PT99314B (en) 1999-04-30

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