Method for producing hydrogen fluoride

Abstract

The present invention provides a novel method for producing hydrogen fluoride, which is capable of using various calcium fluoride sources and preventing a second pasty state from occurring, effectively. In a method for producing hydrogen fluoride by reacting calcium fluoride with sulfuric acid, following steps are conducted: (a) a step for mixing and reacting calcium fluoride particles having an average particle diameter of 1-40 m with sulfuric acid at a sulfuric acid/calcium fluoride molar ratio of 0.9-1.1 under a temperature of 0-70 C. to obtain a solid-state reaction mixture; and (b) a step for heating the solid-state reaction mixture to a temperature of 100-200 C. to react with itself, and thereby producing hydrogen fluoride in a gas phase.

Claims

1. A method for producing hydrogen fluoride by reacting calcium fluoride with sulfuric acid, which comprises: (a)(1) conducting raw-material mixing and reacting of calcium fluoride particles having an average particle diameter of 1-40 m and sulfuric acid at a sulfuric acid/calcium fluoride molar ratio of 0.9-1.1 under a temperature of 0-40 C. to form a first mixture, (a)(2) then heating the first mixture to a temperature higher than the temperature of the raw-material mixing but not higher than 70 C. so that the calcium fluoride particles and sulfuric acid react and form a solid-state reaction mixture; and (b) heating the solid-state reaction mixture to a temperature of 100-200 C. to react with itself, and thereby produce hydrogen fluoride in a gas phase, wherein the reaction mixture remains in the solid state during said heating of the solid-state reaction mixture.

2. A method for producing hydrogen fluoride by reacting calcium fluoride with sulfuric acid, which comprises: (a)(1) conducting raw-material mixing and reacting of calcium fluoride particles having an average particle diameter of 1-40 m and sulfuric acid at a sulfuric acid/calcium fluoride molar ratio of 1.1-2.2 under a temperature of 0-40 C. to form a first mixture, (a)(2) then heating the first mixture to a temperature higher than the temperature of the raw-material mixing but not higher than 70 C. so that the calcium fluoride particles and sulfuric acid react to form a solid-state reaction mixture; and (b)(1) adding and mixing calcium fluoride particles having an average particle diameter of 1-40 m to and with the solid-state reaction mixture at a sulfuric acid/calcium fluoride molar ratio of 0.9-1.1 in total for steps (a)(1), (a)(2) and (b)(1) to form a second mixture, and (b)(2) then heating the second mixture to a temperature of 100-200 C. to react with itself, and thereby producing hydrogen fluoride in a gas phase, wherein the reaction mixture remains in the solid state during said heating of the second mixture.

3. The method according to claim 1, wherein the calcium fluoride particles comprise fluorite, recovered or synthesized calcium fluoride, or a mixture of the fluorite and calcium fluoride.

4. The method according to claim 2, wherein the calcium fluoride particles comprise fluorite, recovered or synthesized calcium fluoride, or a mixture of the fluorite and calcium fluoride.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a schematic view for explaining the conventional method for generating hydrogen fluoride.

DESCRIPTION OF EMBODIMENTS

Embodiment 1

(2) This embodiment relates to the method for producing hydrogen fluoride in the first aspect of the present invention.

(3) First, calcium fluoride particles are prepared. The calcium fluoride particles shall have an average particle diameter of 1-40 m. Due to the average particle diameter of the calcium fluoride particles being not smaller than 1 m, the reaction mixture can be solidified with an appropriate velocity in the step (a) (or, a homogeneous solid-state reaction mixture can be obtained while preventing the solidification from proceeding excessively rapidly). Due to this diameter being not larger than 40 m, it is able to effectively avoid occurrence of the second pasty state in the step (b). The average particle diameter of the calcium fluoride particles is preferably 5-30 m. Due to this diameter being not smaller than 5 m, it is able to prevent the reaction velocity from being too fast. Due to this diameter being not larger than 30 m, it is able to surely avoid occurrence of the second pasty state.

(4) For the calcium fluoride particles, any calcium fluoride source can be used as long as it has such average particle diameter. For example, it may be fluorite, recovered or synthesized calcium fluoride by chemical processes or the like, and may be those subjected to operation such as purification and/or grinding. In a case of using fluorite as the calcium fluoride particles, fluorite may be of any locality, for example, may be from China, Mexico, South Africa or others. The calcium fluoride particles have only to contain calcium fluoride as a main component, and may contain impurities such as silicon dioxide (SiO.sub.2), calcium carbonate (CaCO.sub.3), phosphorous (P), arsenic (As), calcium chloride (CaCl.sub.2) and so on. The purity of the calcium fluoride particles is not specifically limited, but preferably 90% by weight or more, and more preferably 95% by weight or more.

(5) For sulfuric acid, concentrated sulfuric acid, e.g. concentrated sulfuric acid of about 98% or more, can be used, generally. However, it is not limited thereto. For example, combinations of oleum (SO.sub.3 and H.sub.2SO.sub.4) and water, of sulfur trioxide (SO.sub.3) and water, of oleum and sulfur trioxide (SO.sub.3) and water can be used to prepare sulfuric acid.

(6) Step (a)

(7) The calcium fluoride particles and sulfuric acid are mixed together (or stirred), positively (in other words, intentionally, for example, by adding external force, which also applies hereinafter), of which amounts satisfy a sulfuric acid/calcium fluoride molar ratio of 0.9-1.1. Depending on kinds of impurities in the calcium fluoride particles, for the purpose of compensate consumption of sulfuric acid by the impurities, sulfuric acid and/or SO.sub.3 may be charged with an excess amount corresponding to the consumption. While the mixing has only to be conducted at a temperature of 0-70 C., the temperature is preferably increased after raw-material mixing.

(8) The raw-material mixing can be conducted at a temperature of 0-40 C. Due to the temperature being not less than 0 C., sulfuric acid can be retained at a liquid state without freezing. Due to the temperature being not larger than 40 C., this can slow the reaction rate of the formula (1), sufficiently. Thus, a mixture can be obtained in the form of a substantially homogeneous slurry, while the reaction of the formula (1) is prevented. The temperature of the raw-material mixing is more preferably 0-30 C. Due to the temperature being not larger than 30 C., it is able to prevent the raw-material mixture from solidifying during the mixing. It is desirable to conduct the raw-material mixing, promptly. When the time period thereof is not larger than 20 minutes, the raw-material mixture can be prepared uniformly, before it solidifies.

(9) After the raw-material mixing, the resultant slurry mixture (raw-material mixture) is heated to a temperature which is higher than the temperature for the raw-material mixing but not larger than 70 C. By increasing the temperature of the raw-material mixture, the reaction rate of the formula (1) can be increased. Due to the temperature being not larger than 70 C., a reaction mixture can be homogeneously solidified at an appropriate rate while the risk of corrosion by sulfuric acid is alleviated, and this is also convenient for easier control in operation. Thus, the reaction of formula (1) proceeds to spent sulfuric acid in a liquid state and generate Ca(HSO.sub.4).sub.2 in a solid state. During this time, the raw-material mixture changes its form from slurry to solid, and therefore scraping (or stirring or mixing) of the mixture is desirably conducted to prevent it from adhering to the reactor. The heating temperature may vary depending on the temperature for the raw-material mixing, it is more preferably 20-50 C. Due to the heating temperature being not less than 20 C., it is able to attain a practically preferable time period for solidification. Due to the heating temperature being not larger than 50 C., the corrosion can be further suppressed. The heating time may be, for example, 1-40 minutes. Due to it being not shorter than 1 minute, the sufficient time period for solidification can be obtained. Due to it being not longer than 40 minutes, this can prevent the apparatus from becoming too large in scale. Hydrogen fluoride concurrently generated may exist in the gas phase or in the solid mixture. Hydrogen fluoride existing in the gas phase is preferably recovered to be purified and separated as the aimed product.

(10) Thus, a solid-state reaction mixture which is preferably homogeneous can be obtained. The resultant solid-state reaction mixture contains generated Ca(HSO.sub.4).sub.2 and unreacted CaF.sub.2 at almost equimolar amounts. The conversion ratio of CaF.sub.2 at this time may be 50%5%, although it may vary depending on specific reaction conditions.

(11) Step (b)

(12) The solid-state reaction mixture obtained in the above described step (a) is heated to a temperature of 100-200 C. Due to the temperature being not less than 100 C., hydrogen fluoride can be obtained in a gas phase with a sufficient evaporation rate. Due to the temperature being not larger than 200 C., pyrolysis or evaporation of sulfuric acid can be prevented. The calcium fluoride particles contained in the solid-state reaction mixture have the average particle diameter of 1-40 m and made homogeneous by the mixing, so that even at such lower temperature than that in conventional method the reactions of the formulae (2) and (3) proceed and the reaction rate of the formula (3) is larger than that of the formula (2). Therefore, sulfuric acid in a liquid state which is generated by the formula (2) is immediately spent by reacting with the unreacted calcium fluoride existing in the reaction mixture, and the reaction mixture can remain in the solid state as a whole. During this time, it is not preferable to positively mix (or stir) the reaction mixture since unwanted powder dust is dispersed in the gas phase and involved with hydrogen fluoride. However, the mixing (or stirring) may be conducted when gypsum generated as a by-product is wanted to be obtained in the form of fluidity (powder). It is preferable that the larger the average particle diameter of the calcium fluoride particles is within the range of 1-40 m, the lower the heating temperature is within the range of 100-200 C. The heating temperature is more preferably 100-160 C. Due to the temperature being not larger than 160 C., the corrosion can be prevented. The heating time may be, for example, 10-60 minutes. Due to it being not shorter than 10 minute, hydrofluoric acid can evaporate, sufficiently. Due to it being not longer than 60 minutes, this can prevent the apparatus from becoming too large in scale. Hydrogen fluoride thus generated can be obtained in the gas phase, and is preferably recovered to be purified and separated as the aimed product.

(13) Thus, it is able to obtain hydrogen fluoride in the gas phase while effectively preventing the second pasty state from occurring. The residue of the reaction mixture is in a solid state and may mainly contain gypsum as the by-product. The conversion ratio of CaF.sub.2 at this time may reach 90% or more and preferably 95% or more, although it may vary depending on specific reaction conditions.

Embodiment 2

(14) This embodiment relates to the method for producing hydrogen fluoride in the second aspect of the present invention. This will be hereinafter described focusing on different points from Embodiment 1, and similar explanations to Embodiment 1 will apply to this embodiment unless otherwise specified.

(15) Also in this embodiment, calcium fluoride particles having an average particle diameter of 1-40 m are used, and any calcium fluoride source can be used as long as it has such average particle diameter.

(16) Step (c)

(17) The calcium fluoride particles and sulfuric acid are mixed together (or stirred), positively, of which amounts satisfy a sulfuric acid/calcium fluoride molar ratio of 1.1-2.2. While the mixing has only to be conducted at a temperature of 0-70 C., the temperature is preferably increased after raw-material mixing wherein the calcium fluoride particles and sulfuric acid are mixed together at the sulfuric acid/calcium fluoride molar ratio of 1.1-2.2. The sulfuric acid/calcium fluoride molar ratio is preferably 1.1-2.0. Due to this molar ratio being not larger than 2.0, it is able to substantially eliminate unreacted sulfuric acid. As for the rest, they are similar to the step (a) in Embodiment 1.

(18) Thus, a solid-state reaction mixture which is preferably homogeneous can be obtained. The resultant solid-state reaction mixture may contain generated Ca(HSO.sub.4).sub.2 and unreacted CaF.sub.2, and the ratio of the unreacted CaF.sub.2 may vary depending on the sulfuric acid/calcium fluoride molar ratio of the raw materials. When the sulfuric acid/calcium fluoride molar ratio of the raw materials is high (for example, 2.0-2.2), substantially non-existence of the calcium fluoride particles is possible. The conversion ratio of CaF.sub.2 at this time is within the range of about 50% to 100%, depending especially on the sulfuric acid/calcium fluoride molar ratio of the raw materials.

(19) Step (d)

(20) The solid-state reaction mixture obtained in the above described step (c) is added with calcium fluoride particles having an average particle diameter of 1-40 m. The amount of the additional calcium fluoride particles is selected so that the sulfuric acid/calcium fluoride molar ratio in total of the steps (c) and (d) results in 0.9-1.1. The additional calcium fluoride particles may be from a calcium fluoride source which is either the same as or different from that used in the step (c). After the calcium fluoride particles are added to the above described solid-state reaction mixture, they are mixed (or stirred) together, positively to obtain a mixture which is preferably homogeneous (added mixture, which is also in a solid state). Then, thus resultant added mixture is heated to a temperature of 100-200 C. As for the rest, they are similar to the step (a) in Embodiment 1.

(21) Thus, also in this embodiment, it is able to obtain hydrogen fluoride in the gas phase while effectively preventing the second pasty state from occurring. The residue of the reaction mixture is in a solid state and may mainly contain gypsum as the by-product. The conversion ratio of CaF.sub.2 at this time may reach 90% or more and preferably 95% or more, although it may vary depending on specific reaction conditions.

EXAMPLES

Examples 1-3

(22) These Examples 1-3 relate to the method for producing hydrogen fluoride in the first aspect of the present invention.

(23) Step (a)

(24) As calcium fluoride (CaF.sub.2) particles, fluorites from China having various average particle diameters shown in Table 1 were used. The calcium fluoride particles and sulfuric acid were separately located in a thermostatic chamber set at 40 C. to prepare them settled at the temperature in the thermostatic chamber. A weight of the calcium fluoride particles and a weight of sulfuric acid which were used (and therefore a sulfuric acid/calcium fluoride molar ratio) were almost same for Examples 1-3.

(25) In this thermostatic chamber, the prepared fluorite was charged into a vessel made of PFA (tetrafluoroethylene-perfluoroalkylvinyl ether copolymer) and sulfuric acid was poured thereon gently.

(26) After sulfuric acid was poured, the fluorite and sulfuric acid were stirred with the use of a stirring rod to obtain a raw-material mixture in the form of a homogeneous slurry. The mixing temperature was considered as the temperature set for the thermostatic chamber.

(27) The slurry raw-material mixture was subsequently left at rest. Whether (with the progress of the reaction during this time) the reaction mixture became solidified (a solid-state reaction mixture was obtained) or not was visually observed, and a time period from a time point of pouring sulfuric acid to a time point of the reaction mixture becoming solidified was determined as an initial solidification time period t.

(28) Step (b)

(29) Promptly after solidification, the reaction mixture obtained in the step (a) was transferred to a vessel lined with a fluororesin and controlled at a predetermined temperature, and stirred with the use of a stirring rod.

(30) While the stirring was continued, whether (with the progress of the reaction during this time) the reaction mixture became pasty again (the second pasty state occurred) along the way or not was visually observed.

(31) During this time, hydrogen fluoride was produced in a gas phase.

(32) As to Example 1, a time period from a time point of transferring the reaction mixture obtained in the step (a) to the vessel to a time point of finishing the production of hydrogen fluoride from the reaction mixture was determined as a high temperature reaction time period, and it was 50 minutes.

(33) Operation conditions and results for the respective examples are shown in Table 1. In the table, weights of CaF.sub.2 particles and sulfuric acid are net weights of CaF.sub.2 and sulfuric acid, and H.sub.2SO.sub.4/CaF.sub.2 (mol/mol) means a sulfuric acid/calcium fluoride molar ratio used in the step (a). As to the results of observation whether it became Solidified or not, a case of becoming solidified is shown as Solidified and a case of not becoming solidified is shown as No. As to the results of observation whether the Second pasty state occurred or not, a case of occurrence is shown as Yes and a case of no occurrence is shown as No. (These also apply to other tables.)

(34) In Examples 1-3, a solid-state reaction mixture was obtained in the step (a), and occurrence of the second pasty state was not observed in the step (b).

Comparative Examples 1 and 2

(35) These Comparative Examples 1 and 2 are comparative examples to the method for producing hydrogen fluoride in the first aspect of the present invention, and used calcium fluoride particles having average particle diameters equal to and larger than the upper limit for the range of the average particle diameter in the present invention.

(36) Similar procedures to Example 1 were carried out, except that an average particle diameter of calcium fluoride particles used as the raw material and a heating temperature (reaction temperature) in the step (b) were changed. A weight of the calcium fluoride particles and a weight of sulfuric acid which were used (and therefore a sulfuric acid/calcium fluoride molar ratio) were almost same as Example 1.

(37) Operation conditions and results for these Comparative Examples 1 and 2 are shown in Table 1.

(38) In Comparative Example 1, where the calcium fluoride particles having the average particle diameter of 40 m was used in the step (a), a solid-state reaction mixture was obtained in the step (a), but occurrence of the second pasty state was observed in the step (b). This is because the heating temperature in the step (b) was too high.

(39) In Comparative Example 2, even after 40 minutes had passed from the time point of pouring sulfuric acid in the step (a), the reaction mixture did not became solidified. In the step (b), the reaction mixture obtained in the step (a) in the form of a slurry was transferred as it is to a vessel lined with a fluororesin and controlled at 110 C., and stirred with the use of a stirring rod, resulting in the reaction mixture solidified. In the step (b), a time period from a time point of transferring the reaction mixture in the form of a slurry to the vessel to a time point of the reaction mixture becoming solidified was determined as a post-heating solidification time period, and it was 0.8 minute. After the reaction mixture became solidified, whether it became pasty again (the second pasty state occurred) along the way or not was visually observed. As a result, the second pasty state was observed.

Comparative Example 3

(40) This Comparative Example is a comparative example to the method for producing hydrogen fluoride in the first aspect of the present invention, and did not conduct mixing in the step (a).

(41) Similar procedures to Example 1 were carried out, except that after sulfuric acid was poured, a resultant was not subjected to sufficient stirring, but subsequently left at rest. A weight of the calcium fluoride particles and a weight of sulfuric acid which were used (and therefore a sulfuric acid/calcium fluoride molar ratio) were almost same as Example 1.

(42) Operation conditions and results for this Comparative Example are shown in Table 1. In this Comparative Example, a solid-state reaction mixture was obtained in the step (a), but occurrence of the second pasty state was observed in the step (b).

(43) TABLE-US-00001 TABLE 1 Step (a) CaF.sub.2 particles Initial Average Sulfuric solidification particle acid H.sub.2SO.sub.4/ time Step (b) diameter Weight Weight CaF.sub.2 Temperature period Temperature Second (m) (g) (g) (mol/mol) ( C.) Solidified (minutes) ( C.) pasty Example 1 8 3.80 5.11 1.07 40.0 Solidified 12 140 No Example 2 34 3.80 4.85 1.02 40.0 Solidified 38 200 No Example 3 40 3.90 5.10 1.04 40.0 Solidified 40 110 No Comparative 40 3.90 5.23 1.07 40.0 Solidified 40 210 Yes Example 1 Comparative 56 3.80 5.23 1.10 40.0 No 110 Yes Example 2 Comparative 8 3.80 5.01 1.05 40.0 Solidified 16 140 Yes Example 3 (no mixing)

Example 4

(44) This example is a modified example from Example 1, and used a mixture of two kinds of particles for a material of calcium fluoride particles as the raw material.

(45) In the step (a), a mixture of 1.90 g of fluorite from China having an average particle diameter of 34 m and 1.90 g of recovered calcium fluoride particles having an average particle diameter of 17 m was used as calcium fluoride (CaF.sub.2) particles. This recovered calcium fluoride was obtained by letting water absorb hydrogen fluoride (HF) which was generated by thermal decomposition of fluorine containing compounds, neutralizing it with slaked lime (Ca(OH).sub.2) to produce calcium fluoride (CaF.sub.2), adding a coagulating agent to a resultant slurry solution to concentrate and precipitate calcium fluoride, separating it from water and then drying it. Except for these, similar procedures to Example 1 were carried out. A total weight of the calcium fluoride particles and a weight of sulfuric acid which were used (and therefore a sulfuric acid/calcium fluoride molar ratio) were almost same as Example 1.

(46) Operation conditions and results for this Example are shown in Table 2. Also in this Example, a solid-state reaction mixture was obtained in the step (a), and occurrence of the second pasty state was not observed in the step (b).

(47) TABLE-US-00002 TABLE 2 Step (a) CaF.sub.2 particles Initial Average Sulfuric solidification particle acid H.sub.2SO.sub.4/ time Step (b) diameter Weight Weight CaF.sub.2 Temperature period Temperature Second (m) (g) (g) (mol/mol) ( C.) Solidified (minutes) ( C.) pasty Example 4 34 + 17 1.90 + 1.90 4.79 1.00 40.0 Solidified 3 140 No

Example 5

(48) This example relates to the method for producing hydrogen fluoride in the second aspect of the present invention.

(49) For the step (c), 1.95 g of calcium fluoride reagent having an average particle diameter of 13 m (manufactured by Wako Pure Chemical Industries, Ltd.) was used as calcium fluoride (CaF.sub.2) particles together with 5.40 g of sulfuric acid, and a temperature was set at 0 C. A reaction mixture solidified in the step (c) was added with 1.95 g of fluorite from China having an average particle diameter of 40 m as calcium fluoride (CaF.sub.2) particles, and stirred with the use of a stirring rod, sufficiently. In the step (d), the reaction mixture thus obtained was transferred to a vessel lined with a fluororesin and controlled at 120 C., and stirred with the use of a stirring rod. Except for these, similar procedures to the step (a) and the step (b) in Example 1 were carried out to conduct the step (c) and the step (d), respectively.

(50) Operation conditions and results for this Example are shown in Table 3. In the table, Total H.sub.2SO.sub.4/CaF.sub.2 (mol/mol) means a sulfuric acid/calcium fluoride molar ratio in total used in the step (c) and the step (d). Also in this Example, a solid-state reaction mixture was obtained in the step (c), and occurrence of the second pasty state was not observed in the step (d).

Comparative Example 4

(51) This Comparative Example is a comparative example to the method for producing hydrogen fluoride in the second aspect of the present invention, and conducted addition of calcium fluoride particles having a larger average particle diameter in the step (d).

(52) Similar procedures to Example 5 were carried out, except that an average particle diameter of calcium fluoride (CaF.sub.2) particles added in the step (d) was changed and a heating temperature was set at 160 C. A weight of the calcium fluoride particles and a weight of sulfuric acid which were used in the step (c) (and therefore a sulfuric acid/calcium fluoride molar ratio) were almost same as Example 1.

(53) Operation conditions and results for this Comparative Example are shown in Table 3. In this Comparative Example, a solid-state reaction mixture was obtained in the step (c), but occurrence of the second pasty state was observed in the step (d).

(54) TABLE-US-00003 TABLE 3 Step (c) Step (d) CaF.sub.2 particles Initial CaF.sub.2 particles Average Sulfuric solidification Average Total particle acid H.sub.2SO.sub.4/ time particle H.sub.2SO.sub.4/ Tem- diameter Weight Weight CaF.sub.2 Temperature period diameter Weight CaF.sub.2 perature Second (m) (g) (g) (mol/mol) ( C.) Solidified (minutes) (m) (g) (mol/mol) ( C.) pasty Example 5 13 1.95 5.40 2.20 0.0 Solidified 1.5 40 1.95 1.10 120 No Comparative 13 1.91 4.90 2.04 0.0 Solidified 1.6 85 1.90 1.02 160 Yes Example 4

INDUSTRIAL APPLICABILITY

(55) The method for producing hydrogen fluoride of the present invention can be used to replace the conventional method for producing hydrogen fluoride, and is able to largely alleviate practical restrictions on the calcium fluoride source and the operation conditions and to effectively prevent the second pasty state from occurring.

REFERENCE SIGNS LIST

(56) 1 Preliminary reactor 3 Induction pipe 5 Rotary kiln