JPS62235235A - Method for protecting glass device from hydrofluoric acid - Google Patents

Abstract

PURPOSE:To protect a glass device from the corrosion of hydrofluoric acid by allowing group IIIA and IVB elements or their compds. to exist in the system. CONSTITUTION:Group IIIA and IVB elements (e.g., B, Al, Ti, Zr, etc.) or their compds. (e.g., B2O3, Al2O3, TiO2, ZrO2, etc.) are allowed to exist in a reaction or a treating stage wherein hydrofluoric acid is present or generated. Even when glass device is used, the glass is never deteriorated or slightly deteriorated, and the industrial use of the glass device is made possible.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention protects glass equipment from the corrosive effects of hydrofluoric acid in chemical reactions or processing steps in which hexafluoric acid is present or generated.
The purpose is to enable industrial use.

[Prior art]

When hydrofluoric acid is present or generated in chemical reaction equipment, treatment equipment tanks, etc. made of glass, no effective means for protecting the glass from the corrosive action of hydrofluoric acid is known. However, conventionally, this type of method was
describes that adding silica gel during bromination of trifluoromethylbenzene can prevent corrosion of the equipment. This method has problems in its use, as the effect is not reliable enough to allow the glass to be used for a long period of time. This may be related to the cause, but if even a small amount of water is present in the system, the corrosion of glass becomes more severe. USP 4401623 describes adding calcium chloride in exactly the same system, but
This is also the same, and it is not possible to obtain a satisfactory effect to the extent that it is carried out industrially.

[Problem that the invention seeks to solve]

In recent years, fluorine-based organic compounds have been increasingly used in medicines, agricultural chemicals, polymeric materials, and the like. The importance of manufacturing technology for these organic compounds is also increasing. It is known that some organic fluorine compounds undergo a partial dehydrofluorination reaction when handled, and the generated hydrofluoric acid corrodes the glass parts of manufacturing equipment. For example, acidic diazolysis reaction of 70-roanilines, hydrolysis reaction of esters having a trifluoromethyl group, 1-tolation of compounds having a trifluoromethyl group or a fluorine atom,... rogenation, sulfonation reaction,
It is known for the dealkylation reaction of fluorine-containing phenol, phenetol, etc. with hydrogen bromide water. or,
The same applies to the step of concentrating water contained in unstable fluorine W molecules, such as trO-fluoronitrobenzene, polyhalogenated o-nitrofluorobenzene, etc., in a dehydrated organic solvent.

By the way, in the chemical industry, glass is frequently used as a material for chemical-resistant chemical equipment. Glass is usually used in the form of a glass lining. However, the most powerful corrosive agent for glass is hydrofluoric acid. Therefore, it is difficult to make full use of glass materials under conditions where hydrofluoric acid is present or generated.

Therefore, expensive metals or alloys such as tantalum, monel, and barsteroid alloys must be used. Therefore, in the chemical industry, it has been a long-held desire to protect glass from the corrosive effects of hydronic acid. As a result of repeated studies, the present inventors have found that even in the presence of hydrofluoric acid, the present invention can be manufactured using glass materials without any problems, and the periodic law length is 11.
The present invention relates to a method for protecting a glass device from the corrosive action of hydrofluoric acid, characterized by the presence of elements of groups A and B or their compounds in the system. More specifically, examples include alcohols, esters, halogenated hydrocarbons, ethers, aliphatic hydrocarbons, ketones, aromatic hydrocarbons, aliphatic amines, aromatic amines, aliphatic carboxylic acids, aromatic carboxylic acids, and phenols. , in an organic medium such as an aprotic polar solvent, or in an inorganic medium such as water, sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, chlorosulfonic acid, phosphoric acid, or a mixed medium thereof. To protect glass equipment from hydrofluoric acid during chemical reactions or processing steps that occur, the periodic table [[A, ■B
For example, B, At, Ga, In, Tl, Ti,
It consists of making an element such as Zr or a compound thereof exist in the system. These compounds may be either organic or inorganic compounds, and may be decomposed by contact with water, acids, bases, etc. in a medium. A specific example is 80% B4O5
, B2O3, hypoboric acid, hypoborate, boric acid, borate, peroxoborate, borate ester, BPO4, B
As04, BCl31 BBr3, BI3% B2C1
4, B2Br4B2I4, B (OCOCH3)3, B
3B O3, (CH3)3B 1(CH3)2BrB
, CH3B(OH)2, CH3BBrz, phBct
z, phB(OH)2, BFe, MT3R4, MBH
4, BHR2, BH2R (R is an alkyl group or aryl group, M is a monovalent metal atom) At(OCH2CH2CH2CH3)3, [:AtH3
), MgH2・2AtH3, L i AtH4, At
203, aluminum phosphate, Az(oH)3, aluminate, AtCl3, AtBr3, aluminum oxalate, Atl3, Al2(SO4)3, aluminum citrate, KAt(504)2・12H20°At203・
3Si02, At(NO3)3, At203・B2O3
, At(SCN)3, At(CH3COO)3, aluminum laurate, basic aluminum acetate, AlC1
,3・NH4C1%AtNH4(SO4)z・12H2
0, AtNa (S 04 )2 ・12H20, AL
Zn(S04)4・24H20, AL2S3, AtH3
, AtR2X, AtRX2 (R = 7 alkyl group or aryl group X = CL%Br%I) T i B2, TiH4, TielTi(OH)z, T
i203, Ti(OH)3, Ti0z, TiCl2,
TiBr2, Ti I2, Ti C13, [Ti (
OH)s)C23, TiBr3, Til3, TiCl4
, TiBr4% TiI4, Ti51Ti2S3, Ti
S2, Ti2(S04)3, T i P 207, Ti
(304)z, Ti(OCH3)4T1CaO3, Ti
(COO)3, Ti (COO)4, TiMgO3,
TiS, TiS2, B2 Ti 03, M[TiC
ts(OH2)], Usu÷皓←oblique←→, MTiCΔW
, monovalent metal atom) Z r02, Z ro2' XH2O, ZrO3.2H
20, ZrC42, K4Zr04・4H20”2H20
, ZrBr4, ZrI2, ZrBrpsZrCL3, Z
rBr3, Zrl3, ZrCl2, ZrL, Zr0C
L2”8H20% Zr203cL2, Zr(NO3)
4・5H20, Zro(NO3)2 ・2H20, Zr
(SO4)z, Zr(SO4)2・4H20, Zr0(
S04), Zr0(H2PO4)2, ZrPz07, Z
rSiO4, Zr(CH3COO)4% Zr0(CH
3COO) z, Z r (IV) Acetylacetonate, ZrAt2, Z rB2, ZrC1zO1L-;-ri, ZrCL209, ZrH2, MZrOa, (M is 1
valent metal atoms), but are not limited to them.

Moreover, they may be used alone or in a mixed system. The amount of effective use is related to the amount of heptose acid. Generally, it is preferable to use it in an amount of 0.5 to 10 times the number of moles of hydrofluoric acid, but it may be used in an even larger amount to enhance the effect. When adding it, it is desirable to choose a substance that is soluble in the system, but if the solubility is poor, grind it to increase the specific surface area and vigorously stir the system to increase the contact efficiency with hydrofluoric acid. good. Alternatively, it may be added after being dissolved in a solvent such as water, alcohol, or benzene. The systems in which the present invention is used include the media listed above, but those of particular industrial value are reactions or handling in acidic media or their aqueous solutions. Examples of the acid include those listed above.

Regarding glasses, the glasses that are particularly effective in the method of the present invention include oxide glasses (5i02, B2O3, GeO2, Ag2O3, Na2
O,5b203,BaO,Bi2O3,v205.5b
205, ZrO2, ZnO1Ti02, etc.). Among them, silicic acid or glass containing silicic acid (alkali silicate glass, soda lime glass, potash lime glass, barium glass A' silicic acid, etc.). However, other materials such as nitrate glass, chloride glass, carbonate glass, etc. may also be used. Examples include Pyrex, Terex (product name borosilicate glass), Vycor (product name quartz glass), enamel with a glass layer baked onto the metal surface, and glass lining material (Ikebukuro Horo Kogyo Co., Ltd. GL-40).
0 etc.).

〔Example〕

Examples are shown below. In addition, the glass test piece in the examples is a microscope slide glass [manufactured by Matsunami Glass Industry ■ JIS
R3703].

Also, all percentages indicate weight %.

Example 1 120 g of 25% sulfuric acid containing 0.28 g of hydrogen fluoride
In addition to m1 Teflon pin, powdered boric acid1
．． Add 8g. Next, put a glass test piece in, close the stopper, and
After stirring at the same temperature for 1 hour, a glass test piece was taken out, washed with water, and dried, and the state of corrosion was observed, and no change was observed in the test piece.

Example 2 40 g of ethanol containing 0.14 g of hydrogen fluoride was added to 12
In addition to the 0ml Teflon pin, add 1.0g of powdered aluminum hydroxide.

Then, the mixture is stirred at 60° C. for 3 minutes. A glass test piece was put in the mixture, the mixture was capped, and the mixture was stirred at the same temperature for 1 hour, and then operated in the same manner as in Example 1. No change was observed in the test piece.

Example 3 120 m of 30 g of xylene containing 0.06 g of hydrogen fluoride
1. In addition to the Teflon pin, powdered Zr(IV) acetylacetonate 1. Add og.

Then, the mixture is stirred at room temperature for 10 minutes. A glass test piece was placed in the mixture, the mixture was stoppered, and the mixture was stirred at 100° C. for 1 hour, and then operated in the same manner as in Example 1. No change was observed in the test piece.

Example 4 20% titanium trichloride instead of boric acid in Example 110.
When 8 g was added and the same operation was performed, no change was observed in the test piece.

The obtained Examples 5 to 21 are shown in the table. However, the glass protective agent was used either completely dissolved or suspended.

Examples 22 to 25 will be similarly shown below.

However, instead of the glass test piece, a glass lining (GL-400) test rod manufactured by Ikebukuro Horo Kogyo Co., Ltd. was used.

Example 27 250 g of 47% hydrobromic acid and P-methoxyfluoroben 9
Put 60 g of glass lining test piece G into the flask.
After applying L-400 (manufactured by Ikebukuro Horo Kogyo Co., Ltd.), the mixture was stirred under heating and reflux for 11 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted three times with 50 g of dichloromethane. Concentrate and P
-41.6 g of fluorophenol was obtained. No change was observed in the test piece.

Similarly, when aluminum hydroxide was not added, severe corrosion was observed in the test piece.

Example 28 (1) 100 g of 95% P-fluoroaniline was added dropwise to an acidic aqueous solution consisting of 100 g of concentrated sulfuric acid and 800 ml of water while adding ice to form a slurry of P-fluoroaniline sulfate. A 30 d% sodium nitrite aqueous solution was added dropwise over about 2 hours while adding ice and keeping the liquid temperature below 7°C. Diazotization was then completed by stirring at the same temperature for 2 hours. Sulfamic acid 1. Excess sodium nitrite was decomposed by adding Og to obtain about 1.2 t of P-fluoroaniline diazonium salt.

(2) 150 g of copper sulfate pentahydrate, 150 g of water, and 4.0 g of aluminum hydroxide were added to a four-piece flask equipped with a condenser, and the same glass test piece as in Example 27 was added thereto, followed by heating and stirring. The diazonium salt described in (1) was added dropwise at a constant rate below the boiling point, and the entire amount was added in about 3 hours. Along with the dropping, water containing p-fluorophenol was distilled out from the condenser. Approximately 1.3 ml of distilled water was obtained.

After adding 260 g of sodium chloride to this and dissolving it completely,
When extracted three times with 200 ml of toluene and analyzed for P-70 phenol content, a yield of 93% was obtained. Same reaction 2
After performing the test 0 times, the test piece was taken out and observed, and no change was observed. For reference, in the same number of experiments conducted without adding aluminum hydroxide, severe corrosion was observed on the test pieces.

Example 29 200 mesh aluminum hydroxide (2,0 g) was added to the P-fluorophenol toluene solution obtained in Example 28, and further rectified in a flask equipped with the same glass test piece as in Example 27. The rectification took 10 hours under reduced pressure at a tower top temperature of 60 to 110°C. After the rectification, the test piece was taken out and observed, and no changes were observed.

Example 30 Pencitrifluoride 70g, AtBra 25g
was placed in a 2t flask, and the same glass test piece as in Example 27 was attached.

About 20 g of bromine was added under stirring at a reaction temperature of 40 to 60°C.
The reaction was carried out dropwise over a period of time. The reaction product was neutralized with an aqueous sodium hydroxide solution, followed by steam distillation, extraction with dichloroethane, concentration, and distillation to obtain 27 g of m-bromobencytrifluoride. After the reaction was completed, the test piece was taken out and observed, and no change was observed.

Example 31 148 g of potassium fluoride ground in a ball mill for 24 hours, 500 ml of sulfolane in a 1 t flask, 2, 3, 4
, 168 g of 5-tetrachloronitrobenzene was added, and 1
After refluxing at 90°C for 6 hours, the mixture was cooled and filtered. F liquid is 2
The mixture was transferred to a T flask, 500 ml of water and 2.0 g of zirconium oxychloride were added thereto, and the same test piece as in Example 27 was attached. Thereafter, steam distillation was performed to obtain about 26 g of distilled water containing 110 g of 3,5-dichloro-2,4-difluoronitrobenzene. No change was observed in the test piece.

Example 32 100 g of ethyl P-trifluoromethylbenzoate and 300 ml of 20% sulfuric acid were added to a 500 ml flask, and a test piece was attached in the same manner as in Example 27. The mixture was heated and stirred for 10 hours while distilling off the by-product ethanol. At this time, the reaction system was replenished with water corresponding to the amount of distillation. After cooling, the precipitated crystals were dried individually and P-trifluoromethylbenzoic acid 8
1.9g was obtained. No change was observed in the test piece.

〔Effect of the invention〕

Is there any change in the glass even if glass equipment is used in reactions or processing steps where hydronic acid is present or generated?
There were very few changes.

Claims (1)

[Claims] 1. A method for protecting glass equipment from the corrosive action of hydrofluoric acid, characterized by the presence of elements of groups IIIA and IVB of the periodic table or their compounds in the system.