JPS63201138A - Production of metal alkoxide - Google Patents

Abstract

PURPOSE:To obtain the titled compound with simplified process at a low cost, by adding an alcohol to an oxygen-containing organic solvent containing extracted metal halide complex, adding ammonia gas to the mixture to produce a metal alkoxide and regenerating the above solvent. CONSTITUTION:An alcohol ROH having an alkoxy group necessary for the production of objective metal alkoxide D is added to an oxygen-containing organic solvent containing a metal halide complex selected from As, Bi, Cd, Ce, Co, Cr, Ga, Ge, In, Hf, Pb, Se, Te, Tl, V and Zn. NH3 gas is added to the mixture to effect metal alkoxylation B and form a metal alkoxide D and an ammonium halide E and, at the same time, the solvent A is regenerated. The objective metal alkoxide D can be produced in high quality with a simplified and energy-saving process compared with conventional process without restriction in the kind of raw materials.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to A3, Bi, Cd, Ce, Co, Cr,
Ga, Gc, T1, Hf, Pb, Se, Te, T
The present invention relates to a method for producing metal alkoxides of L, V and Zn.

[Conventional technology/problems] Conventionally, the above-mentioned metals (As, Bi, Cd, Ce, Co,
C", G sulfate Ge, In, tlr, PJ Se, Te,
As a method for producing alkoxides of TI, (1) and Zn), many methods have been employed in which these metals or metal halides, especially metal chlorides, are used as starting materials. In this method, after adding an alcohol having an alkyl group necessary to produce the desired metal alkoxide to a metal chloride, N I-1,
It is made by adding gas.

^sC4, +3R011+3NH, -85 (OR)13
NH<Cff1DiCj! 3) 3ROH'38H,l→
[1i(OR)s+3Nl14CjICdCj! z”2
R1”2NIIi→Cd(OR), ÷28I1.ClC
oC1a+2R011)2Nfls→Co(OR)z+
2Nll*cffiCrC13+3ROH+3N11s
-Cr(OR>3+3NII4CICeC14+4RO
Ito4NIIs→Ce(OR)n÷4NII, CJ! G
aC+3ROII+3NHs→Ca(OR) 3”3
NH4CJ! GeCl4+4ROII"4NIIs-G
e(OR), +4NI1. CIInCj! a+3RO
11”3NHs→In(OR)*”3Nll*CIH(
C1, +4RO11+4NI+, -Iff(OR>
, +4811. C41'bc1. ÷2R011+2N
H,→pb(ort), ÷2NI1. Cff1Sect
, +4ROIl+4NI12→5e(OR), +
4NI1. CITeCL+4ROII+4NL-Te(
OR)t"4NHacITICbshi4R01+4N!1
．． →T1(OR), ←4N11. CIVC4, +4RO
Il+4811. -V(OR) 4+4NI1. C4'
ZnCZt+2ROII+2NH, -Zn(OR)**
2NI1. C1' In order to produce metal halides, which are the raw materials for these conventional methods, -m must contain these metals (As
, Bi, Cd, Ce, Co, Cr, Ga, Ge
, In, Hf, Pb, Se, Te, T1. V and Z
A method has been adopted in which n) is once produced and then reacted with C1 gas or F2 gas to form a halide such as a metal chloride or metal fluoride.

This conventional method has the disadvantage that the metal halides produced using purified metals are expensive.

There is also a method of using an alloy instead of using a purified metal, but this method has the disadvantage that separation and purification from impurities in the target metal alkoxide is costly.

Another method that does not use refined metals is to mix carbon with oxides and react with halogen gas to produce metal halides.

11f02+4C)2L-11N,+4COO,5Cr
203 +l, 5C+3[1r-+ 2CrBrz
"3C07, nO+C+C1z→ZnC1t + 2C
However, depending on the type of metal, oxychloride is produced as a by-product as shown in the following formula, and there is a drawback that separation and purification costs are increased to produce high-purity halides.

V2O5+3C, 3C12-ZVOCl, +3c.

In this way, in methods that use metal halides as starting materials, the process to produce the starting materials is long and complicated, and expensive C1N gas and F2 gas are used, making the raw materials increasingly expensive. Producing metal alkoxides from such raw materials has the disadvantage that the manufacturing cost becomes high and the advantages of using metal alkoxides are also lost.

[Means for Solving the Problems] The present invention does not produce metal halides using expensive metals as starting materials, but instead produces metal halides at once from naturally occurring mineral resources or resources such as industrial waste. This relates to a method for producing metal alkoxides of high purity.The process is long and consists of three steps: the process of producing purified metals, then the process of producing metal halides, and the process of producing metal alkoxides, as in conventional methods. This overcomes the drawbacks of high raw material costs and high raw material costs.

Therefore, the present invention can be applied to As, Bi, Cd, Ce, Co
, Cr, Ga, Ge, In, tlf, PJ S
An alcohol having an alkyl group necessary for producing the desired metal alkoxide is added to an oxygen-containing organic solvent in which one type of halogenated metal complex selected from the group consisting of e, Te, TI, After adding NH,
A method for producing a metal alkoxide, which comprises adding a gas to perform metal alkoxylation to produce a metal alkoxide and an ammonium halide, and at the same time regenerating an oxygen-containing organic solvent.

[Function] The gist of the present invention is that As, Bi, Cd,
Ce, Co, Cr, Ga, Ge, In, Hf, P
b. An oxygen-containing organic solvent containing extracted one type of metal halide complex selected from the group consisting of Se, Te, Tl, V, and Zn is mixed with anhydrous mirabilite, anhydrous calcium chloride,
An organic solvent by contacting with a desiccant selected from the group consisting of anhydrous magnesium sulfate, anhydrous magnesium chloride, anhydrous potassium chloride, activated alumina, magnesium perchlorate, phosphorus pentoxide, anhydrous potassium carbonate, barium oxide, zeolite, etc. The water physically contained or the H2O contained in the extract is dehydrated, the organic solvent is dried, and then filled with a dry inert gas, which is then necessary to produce the metal alkoxide for the purpose of production. This is a method of producing alcohol by adding an alcohol having an alkyl group.

11^5c14 ・nOrg"3ROH44NH3-*
^5(OR)3+4Ntl+cl+norg11B 1
Dra ・nOrg+3ROII +4NH3-+ B
i (OR)! +4Nl14[1r +nOrgIf
tceclm ・nOrg+4ROHiNHx=C
e(OR)4◆6NH4C1+nOrg11CdCf
s ・nOrg ”2RO1l +3HHs →Cd
(OR) t +3NII s CI +nOrgII
zcocl 4 ・nOrg +2ROII +48
H2−* Co (OR) 2 +4NH4C1+nO
rg11CrBrn ・nOrg+3ROTO4NIIz
-Cr(OR)s”4NHn口r+nOr@11GaC
1'n ・nOrg+3R011+4Nt13-+Ga
(OR)3÷4NH4C? nOrglIGec44 ・
nOrg +3ROTo48113-*Ca (OR)
3 +4Nll, CI +n0rBH211rc
Na ・nOrg+4RO1l"68Hs→Hr (O
R) 4”6NH4C1+nOrgHInBr 4 ・
nOrg+3ROIl +4NI13 →In (OR
) 3 +4NIl 411r )nOrHHPbls
・nOrg+2ROH+3NH,-+Pb(OR)
283811.1+nOrgIt 2SeC1a ・n
Org +4ROIl +6Nll 3→Se (OR
)4 +6Nll 4 C1+nOrgII =TeC
1i ・nOrg +4ROII +68Hz-Te(
OR), +6H1l 4C1+nOrgHTICI
4 ・nOrg +3ROII +4NN , -TI
(OR)3 +4NIl 4 C1+nOrgtlV
cfs-nOrg+4ROH+58H3-+V(OR
)4 +5NI1. C? nOrgIIZnC13・nO
rg +2ROto38113 →Zn (OR) z
+3NII 4 C1+n0rB In the formula, Org represents an oxygen-containing organic solvent, and one or more types are selected and used from among the ether group, ester group, ketone group, amide group, and alcohol group. be able to.

In addition, ROH in the formula represents an alkanol necessary for the metal alkoxide to be produced, such as methanol, ethanol, butanol (including normal, secondary, and tertiary), inpropatol, 11-propatol, decyl alcohol, etc. Various alkanols.

The chemical species of the metal halide complex that is the starting material shown in the above formula is not fixed as shown in the reaction formula, but includes chloride complexes, fluoride complexes, bromide complexes, and iodide complexes.

Even if the chloride complex is the same, it is natural that the chemical species of the metal complex compound differs depending on the halogen ion concentration and H1 ion concentration, and the amount of extracted metal halide complex is limited to the above formula. Please understand that this is not the case.

In addition, each metal (A
s, Bi, Cd, Ce, Co, Cr, Ga,
Ge, In, Hf, Pb, Se, Te, Tl,
When extracting the metal halide complexes of V and Zn), the amount of water co-extracted is not constant and varies depending on the type of organic solvent and the amount of metal halide complexes extracted, but before making the metal alkoxide. When it is necessary to remove the oxygen-containing organic solvent before adding the alkanol, add anhydrous sodium sulfate, anhydrous calcium chloride, anhydrous magnesium sulfate, anhydrous magnesium chloride, anhydrous potassium chloride, activated alumina, magnesium perchlorate, phosphorus pentoxide, anhydrous. This is accomplished by contacting with a desiccant selected from the group consisting of potassium carbonate, barium oxide, zeolites, and the like.

Each gold jK (As, Bi, Cd, Ce, Co,
C", Ga, Ge, In, l-1r, Pb,
For example, halogen metal complexes of Se, Te, TI, 1 and Zn can be produced as follows. One or more extractants selected from the group of ethers, ketones, esters, amides and alcohols are used by contacting the metal halide complex present in an aqueous solution.

AsC14-+1-1"+nOrg→HAsC14・i
orgAsF +−−t−H”+nOrg−HAsF
4 ・norgB i I 4−+ H”+nO
rg-118i I 4 ・norgBiBr 4-
10 H"+nOrg-+HBiBr* ・norg
HCeCZs-+H''+nOrg-+HzCeC11n
orgCdI 2-+ 1(”+nOrg→HCdI
3- norgHCoCL-+H"+nOrg-+1-
1zCoCL・norgCrBr4−+ l−1”+n
Org-ell CrBrn・norgGaC14-
+H"+nOrg-+HGaCL ・norgG e
Cl 4- + H”monorg-* HG eCe
< ・no rgHHrc 1m-+ 114″+ n
o rg-+ H+Hrc 1g ・no rgI n
Br, -+ H"4-n4-n0r I nBr< ・
norgPbI, −+ H”+nOrg+ HP
bI 3 ・norgS IIc l@-+
H"-to no rg-+ II S
bC11no rgSbBr=-+H"+nOrg-
+H8bBra・norgSeC1@-+H”+nOr
g→H3eCt's-norgSeBrs-+H”+n
Org-+H3eBrrnorgTeC15-1-1-
1”+nOrg-+HTeC1s・norgT (lC
14-+ H"-to no rH-+ HT I
c1*・no rgV C1,-+ II
+÷norg-*HVC1'a・norgZnClx-
+H"+nOrg-HznC1z・norgZnBr2
-+ II"-1-norg→tl ZnBr,・no
rm For the chemical species and extracted species of the halide complex ions of each metal above, 1r! /4, but there are chlorides, fluorides, bromides and iodides, and the type of complex varies depending on the concentration of halogen ions, H0 ions, or salting-out agent present. It is well known that the extraction species are different.

The oxygen-containing organic solvent used in the present invention is selected from the following group.

(a) Group of ethers includes diisoamyl ether, diethyl ether, diisopropyl ether, dichloroethyl ether and ethers having forms similar to these.

(b) Ketone group: Includes methylpropylketone, methylpropylketone, methylamylketone, cyclohexanone, methylcyclohexanone and similar ketones.

(c) Group of esters Naturally, diphosphates, acetates, TOPO (lioctylphosphine oxide), etc. and extractants similar to these are also included.

(d) Amide group: All similar amides such as acetamide and amides of C1-C12 aliphatic carboxylic acids are included.

(e) Group of alcohols: Various (normal, secondary, tertiary) alcohols having 4 to 18 carbon atoms.

The solvent used in the present invention for washing the solid by-product ammonium halide is selected from the following group.

■For petroleum hydrocarbons, the boiling point of petroleum ether, petroleum benzene, hexane, etc. is 100'C or less, and the surface tension is 2.
Includes 30 dynes/ell or less at 0°C.

■For aromatic hydrocarbons, benzene etc. are used.

The desiccant used in the present invention is used to remove physically mixed water and water extracted together with metal halide substances before evaporation and distillation. Molecular sieves such as magnesium sulfate, anhydrous magnesium chloride, anhydrous potassium chloride, activated alumina, magnesium perchlorate, phosphorus pentoxide, anhydrous potassium carbonate, barium oxide, and synthetic zeolites can be used.

The inert gas used in the present invention is N2 gas or A
It is a gas and can be introduced as appropriate in the drying process to expel the atmosphere in the oxygen-containing organic solvent, and
In the heating/evaporation or heating/distillation process, it can be used to constantly fill the inside of the apparatus with an inert gas in order to prevent oxidation of the oxygen-containing organic solvent or the separated metal alkoxide.

The present invention will be described below based on the drawings, but it should be understood that the present invention is not limited thereto.

The flow sheet in Figure 1 shows the basic form of the present invention.
Oxygen-containing organic solvent containing a metal halide complex (A
> is led to the alkoxylation reaction step (B), an alcohol having an alkyl group necessary to produce the desired metal alkoxide is added, and NH3 gas is introduced to produce the metal alcohol.

Next, in a washing/filtration step (C), ammonium halide (E) is separated to obtain metal alkoxide (D).

The flow sheet in Figure 2 is for each metal (As, Bi, Cd,
Ce, Co, Cr, Ga, Ge, In, Hf,
The organic solvent (A) containing the metal halide complexes (Pb, Se, Te, Tl, V, and Zn) is led to the alkoxylation reaction step (B), and the organic solvent (A) containing the metal halide complexes of After adding the alkanol having an alkyl group and, if necessary, also adding a hydrocarbon solvent, NI gas is introduced to generate a metal alkoxide.

Next, in the washing/filtration step (C), after separating the ammonium halide (E), the heating/evaporation or heating/distillation step (F) is performed, where the ammonium halide (E) is filled with inert gas as necessary.
In this step, regenerated oxygen-containing organic solvent (G) and metal alkoxide (D) are obtained.

Excess alkanol and hydrocarbon solvent are recovered and recycled to the alkoxylation reaction step (B) again.

The flow sheet in Figure 3 is the same process as Figure 2 for producing metal alkoxides, but the oxygen-containing organic solvent (A) containing the metal halide complex is added to the alkoxylation reaction step (B). Before dehydration, a dehydration step (H) is carried out to remove co-extracted water and water mixed in as fine water droplets.
In, anhydrous sodium sulfate, anhydrous magnesium sulfate, anhydrous magnesium chloride, anhydrous calcium chloride, anhydrous potassium chloride, activated alumina, magnesium perchlorate, phosphorus pentoxide,
A process operation is incorporated to add a desiccant (J) for contact with a desiccant selected from the group consisting of anhydrous potassium carbonate, barium oxide, zeolites, and the like.

Inert gas is used in the dehydration process (H) and alkoxylation process (B)
and heating/evaporation or heating/distillation step CF) to prevent oxidation of the oxygen-containing organic solvent and the generated alkoxide.

The flow sheet in Figure 4 is for each metal (As, Bi, Cd
, (:6. Co, C", Ga-Ge, In, Hf, P
b, Se.

By contacting an aqueous solution containing metal halide ions of Te, Tl, ■ and Zn) with the regenerated oxygen-containing organic solvent (G) in the extraction step (K), the starting raw material of the present invention can be obtained. This method incorporates a step of producing an oxygen-containing organic solvent (A) containing a metal halide complex.

[Example] The present invention will be further explained with reference to Examples below.

K1 Takumi Table 1 shows the experimental details for each metal.

The test was carried out using samples containing extracted amounts of each metal such that the amount was about 0.1 mole. The amount of added NHs is NHs
I did it a little excessively until it felt like IL.

The oxygen-containing organic solvent containing extracted metal halide complex ions used as a raw material in the present invention is prepared as shown in Table 2 below.

[Effects of the invention] According to the present invention, compared to the case of producing metal alkoxides using conventional methods, the process is simpler, there are no restrictions on raw materials, and the production method is energy-saving, while using expensive raw materials. It is possible to produce metal alkoxides of comparable quality.

[Brief explanation of the drawing]

FIG. 1 is a flow sheet of the basic method of the present invention, and FIG. 2 is a flow sheet of a modified method of the basic method shown in FIG. FIG. 3 is a flow sheet of a modified method including a dehydration step for producing a halogen stopper ILC complex in an aqueous solution and removing co-extracted water when extracted into an organic solvent. This is a flow sheet including a step of using a starting material by bringing a regenerated oxygen-containing organic solvent into contact with an aqueous solution containing a metal halide ion in an extraction step. In the figure: (A) Oxygen-containing organic solvent containing a metal halide complex; (B) Alkoxylation reaction step; (C) Washing/transfer step; (D>Metal alkoxide; (E) Ammonium halide (F) Heating/evaporation or heating/distillation process; (G) Regenerated oxygen-containing organic solvent; (H) Dehydration process; (J) Desiccant; (K) Extraction process. Patent applicant Nishimura Watanabe Extraction Co., Ltd. Laboratory Figure 1 Figure 2

Claims (1)

[Claims] 1. As, Bi, Cd, Ce, Co, Cr, Ga, Ge
, In, Hf, Pb, Se, Te, Tl, V and Zn, which are extracted and contained in an oxygen-containing organic solvent, are necessary for producing the desired metal alkoxide. A method for producing a metal alkoxide, which comprises adding an alcohol having an alkyl group, followed by metal alkoxidation by adding NH_3 gas to produce a metal alkoxide and an ammonium halide, and at the same time regenerating an oxygen-containing organic solvent. 2. Extract the metal halide complex by extracting the oxygen-containing organic solvent containing anhydrous sodium sulfate, anhydrous calcium chloride, activated alumina,
Removal of water in the organic solvent by contacting with a desiccant selected from the group consisting of magnesium perchlorate, anhydrous potassium chloride, anhydrous magnesium sulfate, anhydrous magnesium chloride, phosphorus pentoxide, anhydrous potassium carbonate, barium oxide, and zeolite. A manufacturing method according to claim 1. 3. A patent claim in which the generated ammonium halide is filtered, washed and separated, and then the oxygen-containing organic solvent is regenerated and recovered, and excess alcohol and excess solvent are recovered by heating and evaporating and distilling under reduced pressure or normal pressure. The manufacturing method according to item 1 or 2. 4. Water in the oxygen-containing organic solvent is removed by bringing it into contact with a desiccant, and then heated evaporation and heated distillation are performed under reduced pressure or normal pressure while being filled with an inert gas. The manufacturing method according to any one of Items 1 to 3. 5. In an aqueous solution in which the oxygen-containing organic solvent containing the metal halide complex contains one or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, hydrobromic acid, and hydroiodic acid. As, Bi, Cd, Ce, Co,
Cr, Ga, Ge, In, Hf, Pb, Se, Te, T
Claim 1, which is obtained by bringing one or more metal halide complex ions of L, V, and Zn into contact with an oxygen-containing organic solvent and extracting the complex ions. The manufacturing method according to any one of Items 1 to 4.