JP2003514127A - Transition metal substituted tungstoaluminate complexes for delignification and waste mineralization - Google Patents

Abstract

(57) Abstract A method for delignifying lignocellulosic fibers is disclosed. According to one embodiment, the method has the formula _{[Al l V m Mo n W} o Nb p Ta q (TM) r O s] x- ( wherein, l is 1 to 6, m is 0 18, n is 0 to 40, o is 0 to 40, p is 0 to 10, q is 0 to 10, r is 0 to 9, and TM is d-electron-containing transition. A polyoxometalate complex having an aluminum heteroatom represented by a metal ion (provided that l + m + n + o + p + q ≧ 4, and s is a number large enough to satisfy x> 0) A step of mixing, wherein the obtained composition has a pH of 6 to 11 and a consistency of 1 to 20%, and the obtained composition is subjected to reduction of polyoxometalate in a temperature control and pressure control vessel. And heating under the conditions of temperature and time when delignification occurs. And a step of

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION

The Keggin structure-based heteropolyoxometalates (including their transition metal-substituted derivatives) are homogeneous catalysts that are effective in selectively oxidizing organic and inorganic substrates with a variety of oxidants (MT Pope and A. Mueller, Angew.
Chem. Int. Ed. Enql. 30:34 (1991) and C.I. L. Hill and C.I. M. Prosser-McCartha, Coo
rdination Chem. Rev. 143: 407 (1995)).
Similar to condensed-phase metal oxide catalysts, which are structural and electronic models, many polyoxometallates (POMs) of this type are significantly more stable to oxidizing conditions. Furthermore, by introducing an organic soluble counter cation, many POM anions can be converted to an organic soluble type and used as an organic solvent.

However, many POMs are prone to base hydrolysis, so to use POMs in water, which is the cheapest and safest solvent available, an acidic pH is required.
Often must be limited to values (T. Okuhara, N. Miz
uno and M.D. Misono, Advances in Cat. 41: 113
(1996)). In view of the increasing demand for more environmentally friendly chemical systems, it would be advantageous to develop POMs that are stable in water over a wide pH range. In addition, several salts of the Keggin anion dielectric could potentially be used as antiviral agents (CL Hill, GS Kim, CMP).
Rosser-McCartha, D.R. Judd, In Polyoxomet
alerts: From Platonic Solids to Anti
-Retroviral activity (polyoxometalates: from platonic solids to antiretroviral activity), Pope, M. et al. T. ; Mue
Ller, A .; , Eds. Kluwer Academic Publ
ishers: Dordrecht, Netherlands; pp. Three
59-371, 1994; T. Rhule, C.I. L. Hill, D.A.
A. Judd and R.M. F. Schinazi, Chemical Review
ws, 98: 327 (1988)), and appears to be of value in this regard as it is more stable at physiological pH values (near neutral).

In addition to stability in water, there is a need for a POM oxidation catalyst that can work with the most economical and environmentally advantageous oxidant available, oxygen (O ₂ ). (R. Neumann, M. Dahan, Nature, 388: 353 (
1977)). Here, the POM anion has a positive reduction potential sufficient to rapidly react with the target substrate, and at the same time, it is sufficient for the reaction of the reduced POM anion and O ₂ to proceed rapidly. It is required to be moderately negative (ie preferred both kinetic and thermodynamic) (IA Weinstock)
, Chemical Reviews, 98: 113 (1998)). Neutral pH
The need for both stability in water at values and rapid reactivity with O ₂ is
This is indicated by the report on the xylem delignification catalyst. For example, keguban vanado tungstosilicate ([SiVW ₁₁ O ₄₀ ] ^5- ) is stable at nearly neutral pH values, but its reduction potential is too positive for rapid spontaneous reaction with O _2. (IA
． Weinstock, R.W. H. Atalla, R .; S. Reiner, C.I. H
． Houtman and C.I. L. Hill, Holzforschunq, 52:
304 (1998). On the other hand, [PV ₂ Mo ₁₀ O ₄₀ ] ^5-, in its reduced form, reacts rapidly with O ₂ , but this vanadomolybdophosphate catalyst has a pH above 4.
It is unstable in value (Weinstock, ibid.).

There is a need in the field of delignification of lignocellulosic materials for polyoxometallate compounds that can be stable in water over a broader range of pH values and that can react rapidly with oxygen.

[0005]

[Outline of the Invention]

According to one aspect of the present invention, the general formula _{[Al l V m Mo n W} o Nb p Ta q (TM) r O s] x- ( wherein, l is 1 to 6, m is 0 to 18 And n is 0 to 40, o
Is 0-40, p is 0-10, q is 0-10, r is 0-9, and TM is a d-electron-containing transition metal ion (provided that 1 + m + n + o + p + q ≧
4), s is a number large enough to satisfy x> 0), and a polyoxometallate complex having an aluminum heteroatom is provided.

[0006]   According to another aspect of the invention, it has a Keggin structure and has the general formula [Al_lV_m(TM) _n W_oO_p]^x-(In the formula, 1 is 1 to 2, m is 0 to 6, and n is 0 to 3.
, O is 0 to 12, TM is a transition metal ion containing d electrons (provided that l + m
+ N + o = 12 or 13), and p is a number large enough to satisfy x> 0)
Provided is a polyoxometallate complex having an aluminum heteroatom represented
It

[0007]   One representative polyoxometallate useful in the present invention has the formula [AlVW ₁₁ O₄₀]^6-It is represented by.

According to a further aspect of the invention, there is provided a method of using a derivative of tungstoaluminate of the type described above (mixed additive) as delignifying agent and bleaching agent.

According to a further aspect of the present invention, a substance such as wood pulp, xylem fiber, lignocellulosic fiber and lignocellulosic pulp is contacted with a solution of polyoxometallate complex represented by the above general formula. A method for delignifying the substance, wherein the pH of the solution is 1 to 11, preferably 6 to 11, and more preferably 6 to 11.
9, most preferably adjusted to 7 to 10, the mixture of polyoxometallate and fiber or pulp has a consistency of about 1 to 20%, and the mixture is added to a polyoxometalate in a temperature-controlled and pressure-controlled vessel. Methods are provided for heating under temperature and time conditions in which the metallate is reduced and enhanced delignification occurs.

Preferably, the reduced polyoxometallate complex is selected from the group consisting of air, oxygen, hydrogen peroxide, other organic or inorganic peroxides (free acid or salt form) and ozone. Reoxidize with the oxidant. The most preferred oxidant is oxygen.

According to yet another aspect of the invention, there is provided a method of wet oxidizing a soluble organic lignin or polysaccharide fragment or oxidation product using a polyoxometallate complex of the above general formula. The method involves heating a solution containing both a polyoxometallate and an organic fragment or product in the presence of an oxidizing agent under conditions such that dissolved organic compounds are oxidatively decomposed into volatile organic compounds and water. Including the step of This reaction is preferably carried out in a vessel whose pressure and temperature are controlled. Preferably, the reaction is carried out at a pressure of 10 to 2,000 psi (0.069 to 13.79 MPa) and an ambient temperature of ~ 500 ° C. The pH is preferably 0 to 11, more preferably 6
-11, most preferably 6-9. The oxidant is preferably selected from air, oxygen, hydrogen peroxide, other organic or inorganic peroxides (free acid or salt form) and ozone. The most preferred oxidant is oxygen.

[0012]   According to another aspect of the invention, dodecatungstoaluminate H_Five[AlW₁₂O₄₀
], The pH of sodium tungstate dihydrate solution
7-8, and adjust the aluminum chloride hexahydrate solution to sodium tungstate.
[Al (Al) W] ₁₁ O₃₉]^6-[Al (Al) W by adjusting the pH to about 0.₁₁ O₃₉]^6-To H_Five[AlW₁₂O₄₀], A step of heating under reflux, and H_Five[
AlW₁₂O₄₀] Is isolated, and the method is provided. Also, the present invention
According to H_Five[AlW₁₂O₄₀] Is reacted with a base to give [AlW₁₁O_{3 9} ]^9-Salt is provided. According to a further aspect of the invention, [AlW₁₁O₃₉]^9-
Of AlVW by reacting the salt of₁₁O₄₀]^7-Provided by the salt
To be done. Then, for example, by using bromine, oxygen or ozone, [AlV
W₁₁O₄₀]^7-Oxidize the salt of [AlVW₁₁O₄₀]^6-And

According to yet another aspect of the present invention, a salt of [AlW ₁₁ O ₃₉ ] ^{9- is} reacted with M, where M is manganese (II) or cobalt (II), [
^{_{AlM n W 11 O 39] (}} 9-n) - a method of manufacturing the polyoxometalates complex represented by is provided.

According to yet another aspect of the present invention, a defective structure derivative of an Al-containing polyoxometallate anion (a salt of [AlW ₁₁ O ₃₉ ] ^9- is an example of such a defective structure) Provided is a novel method for producing a polyoxometallate complex represented by the above general formula by reacting with a d-electron-containing transition metal cation to obtain a corresponding d-electron-containing transition metal-substituted polyoxometallate.

A method of delignifying substances such as wood pulp, xylem fiber, lignocellulosic fiber and lignocellulosic pulp is carried out by neutralizing pH 6 to pH 11 or alkaline p.
It is an advantage of the present invention that it can be implemented in an H environment. This is advantageous because lignin is more rapidly oxidized under alkaline conditions and cellulose is less easily hydrolyzed.

[0016] formula _{[Al l V m Mo n W} o Nb p Ta q (TM) r O s] x- ( wherein, l is 1 to 6, m is 0 to 18, n is 0 -40, o is 0-40, p is 0
-10, q is 0-10, r is 0-9, TM is a d-electron-containing transition metal ion (provided that l + m + n + o + p + q ≧ 4), and s is sufficient to satisfy x> 0. It is another advantage of the present invention that polyoxometallate complexes with aluminum heteroatoms represented by a large number) are provided.

The ability of the polyoxometallates to be reoxidized with oxygen is another advantage of the present invention.

Other advantages, features and objects of the present invention will be apparent to those of ordinary skill in the art by reference to the specification, claims and drawings.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION   In general, heteropolytungstates are isostructural heteropolymolybdates.
Greater base stability. This has led to efforts to develop base-stable keguin anions.
Power shows that the focus must be on the development of new polytongue states.
I am inviting. Furthermore, within the Keggin structure type, greater base stability and anion
There is a correlation with the larger negative charge density of D. P. Smith (DP Smith and M.
T. Pope, "Increasing x in the series:
[PV_xW_12-xO₄₀]^{(3 + x)-}, Results in an increase
  in the negative charge on the anion
  and greater hydrostatic stability (series)
: [PV_xW_12-xO₄₀]^{(3 + x)-}Increasing x in
As the negative charge increases, so does the hydrolytic stability). "Inorgani
c Chem. 12: 331, 1973; A. weinstock, R.W. A
． Atalla, R .; S. Reiner, M .; A. Moen, K .; E. Hamm
el, C.I. L. Hill and M.D. K. Harrup, “While [PVW₁₁O ₄₀ ]^Four-  is stable in water at pH values
near 3, the silicon analog, [SiVW₁₁O₄₀]^Five- , Is stable infinitely at relux in
  water initially at pH 7 ([PVW₁₁O₄₀]^Four-Is water
Among them, it is stable at pH values around 3, whereas it is a silicon analogue [SiVW₁₁ O₄₀]^Five-Is stable under reflux in water, which initially has a pH of 7. ”, J. M
ol. Cat. A. Chemical. 116: 59, 1997). Synthetically,
The Keggin anion, which has a larger negative charge density, has a lower valence main group or
Transition metal heteroatom X^{n +}, That is, [X^{n +}W₁₂O₄₀]^(8-n)-To adjust anion from
It can be obtained by manufacturing. The most studied keguin heteropoly
Tungstate anions include phosphorus (P (V), n = 5) or silicon (Si (IV
), N = 4) having a heteroatom as a main component (MT Pope, Hetero).
poly and Isopolyoxometalates (heteropoly and
Isopolyoxometalates), Springer-Verlag, New York
, 1993. Therefore, based on composition and anion charge [AlVW₁₁O₄₀] ^6- Is [PV₂Mo_TenO₄₀]^Five-Or [SiVW₁₁O₄₀]^Five-Greater base stability than
It is expected to have sex. At the same time, [BW₁₁O₃₉]^9-B (III) induction of
The bodies are much less stable than their Si (IV) counterparts. The reason for this is
B (III) is too small [W₁₁O₃₉]^12-The pseudo-tetrahedron part in the shell
This is because it may not be possible to occupy optimally. Al (III) is B (I
II), the present inventors₁₂O₄₀]^Five-And its derivatives
We thought that it would realize greater stability and versatility. However, [A
lW₁₂O₄₀]^Five-Since their derivatives are unknown, their stability is reliably predicted.
could not.

[0020]   Also, there is a correlation between the reduction potential and the anion charge density, and a larger negative
Anions with a charge density have a more negative reduction potential. [SiVW₁₁O₄₀] ^Five- Since the reduction potential is overly positive, it is in its reduced form [SiVW₁₁O₄₀]^6-Is O ₂ Because it cannot react quickly with [AlVW₁₁O₄₀]^6-Is a reduced form of [AlV
W₁₁O₄₀]^7-Due to the more negative reduction potential, O₂React with
Will.

A) Polyoxometallate Complex with Aluminum Hetero Atom According to one embodiment of the present invention, a compound represented by the general formula [Al ₁ V _{m Mn} W _o Nb _p Ta _q (TM) _r O _s ] ^x- (formula In the above, 1 is 1 to 6, m is 0 to 18, n is 0 to 40, and o
Is 0-40, p is 0-10, q is 0-10, r is 0-9, and TM is a d-electron-containing transition metal ion (provided that 1 + m + n + o + p + q ≧
4), s is a number large enough to satisfy x> 0), and a polyoxometallate complex having an aluminum heteroatom is provided.

[0022]   According to another aspect of the invention, it has a Keggin structure and has the general formula [Al_lV_m(TM) _n W_oO_p]^x-(In the formula, 1 is 1 to 2, m is 0 to 6, and n is 0 to 3.
, O is 0 to 12, TM is a transition metal ion containing d electrons (provided that l + m
+ N + o = 12 or 13), and p is a number large enough to satisfy x> 0)
Provided is a polyoxometallate complex having an aluminum heteroatom represented
It

[0023]   One representative polyoxometallate useful in the present invention has the formula [AlVW ₁₁ O₄₀]^6-It is represented by.

In another embodiment, the present invention uses a novel high-yield synthetic method of H ₅ [AlW ₁₂ O ₄₀ ] (JA Mair and JLT Waugh, “Preparatio”.
_{n of H 5 [AlW 12 O} 40] (H 5 [AlW 12 O 40] ( Preparation of incorrectly described as 11-tongue store Rumin acid))] ", J. Chem. Soc. 237
2, 1950; W. Akitt and A. Farthing, "Prepar
ation and ²⁷ Al NMR spectroscopy of H ₅
[AlW ₁₂ O ₄₀ ] (H ₅ [AlW ₁₂ O ₄₀ ] (Mostly a mixture of α and β isomers) and ²⁷ Al NMR spectroscopy). C. S. Dalton Tr
ans. 1615, 1981; H. Brown, "X-ray powder
r diffractometry of Cs ₅ [AlW ₁₂ O ₄₀ ] (Cs ₅ [A
X-ray powder diffraction of 1W ₁₂ O ₄₀ ]) J. Chem. Soc. 3281, 1962; K
． Nomiya and M.M. Miwa, “IR spectroscopy of of
_{H [(C 4 H 9)} 4 N] 4 [AlW 12 O 40] (H [(C 4 H 9) 4 N] 4 IR spectroscopy [AlW ₁₂ O _40]) ", Polyhedron 2: 955,1983 ), And the first reported synthesis of the monolacunary derivative itself [AlW ₁₁ O ₃₉ ] ^9- . The latter are precursors of various transition metal substituted keguin anions, and these [Al
VW ₁₁ O _40] ^7-, and [AlMnW ₁₁ O _39] ^7-, and [AlCoW ₁₁ O _39] ^7- some preparations of, given as an example.

A useful property of aluminum heteroatoms is that ²⁷ Al isotopes present at 100% abundance and having a nuclear spin of 5/2 are easily and rapidly observed by nuclear magnetic resonance (NMR) spectroscopy. Is. Chemical shifts and linewidths of ²⁷ Al NMR signals provide easy access to information about both the coordination number of the aluminum atom and the chemical symmetry of its environment (Akitt, ibid.).

[0026]   Reported [AlW₁₂O₄₀]^Five-In the preparation method of^IIICondensing salt solution
Tang state ([WO_Four]^2-) Slowly in a weakly acidic solution of anions (20 hours)
Must be added dropwise (Mair, Id .; Akitt, Id.). By this operation,
A product mixture forms. Repeated baking and extraction of the reaction residue to
The desired compound is isolated in low yield from the mixture. [XW₁₂O₄₀]^n-(Where X is
Phosphorus (P (V)) or silicon (S) used to prepare P (V) or Si (IV)
Unlike the i (IV)) cation, aluminum (Al (III)) is a heterogen
It can serve both as a child and as an added atom. That is, in the above, [AlW ₁₂ O₄₀]^Five-The product mixture described in the preparation of [Al (Al (Al
) W₁₁O₄₀]^6-(Akitt, ibid .; M. A. Fedott)
ov and L.D. P. Kazanskii, "Solution²⁷Al NMR
spectroscopic of reaction mixes (reaction
Solution of mixture²⁷Al NMR spectroscopy) ", Izv. Akad. Nauk SS
SR, Ser. Khim. , No. 9, 2000-2003, 1988, English translation version
Page 1789).

[0027]   In the above method, the stoichiometry of aluminum is carefully adjusted (2Al: 11W).
Then, the quantitative yield (²⁷Al NMR) at neutral pH [Al (Al) W₁₁O ₃₉ ]^6-To get Aluminum is added dropwise over 90 minutes. Then the initial product
H at pH 0⁺Quantitatively by reacting with (preferably under reflux for 1 week)
In-situ conversion (²⁷Al NMR and crude yield) [AlW₁₂O₄₀]^Five-(
[Al (Al) W₁₁O₃₉]^6-(11/12 mol per 1 mol of). Product
Tungsten-183 NMR spectroscopic analysis showed α- and β-isomers of Keggin structure
It is a mixture with (the β isomer is the main product (80 to 95%))
It The subsequent H_Five[AlW₁₂O₄₀] And the isolation and substitution of additives with transition metal
The synthesis of the mixture with the derivative is carried out by a well-known and established method.

Reagent grade chemicals (sodium tungstate dihydrate, Folin reagent grade) were obtained from commercial sources. Deionized water was used throughout. Infrared and ultraviolet-
Visible spectra were obtained using a Nicolet 510 FTIR and a Hewlett Packard 8452A spectrophotometer, respectively. pH is measured by Orion 250A
Type pH meter was used. Electrochemical data were obtained using a BAS CV-50W electrochemical analyzer equipped with a glass carbon working electrode and an Ag / AgCl reference electrode. The solution used for repeated and differential pulse voltammetry was 0
． It was 1 mM in a sample prepared by dissolving an electrolyte solution of 10 M NaCl in water. The ²⁷ Al and ⁵¹ V NMR spectra described are 130.3 MHz and 131 V, respectively.
． Obtained on a General Electric GN500 MHz spectrometer at 1 MHz. ¹⁸³ W NMR spectrum, Varian UNITY400N
Obtained at 16.66 MHz using MR. The external standards were as follows: ²⁷ A
1, 0.10M AlCl ₃ .6H ₂ O ([Al (H ₂ O) ₆ ] ³⁺ , δ = 0 ppm)
⁵¹ V, 10 mM H ₄ [PVMo ₁₁ O ₄₀ ] (in 0.6 M NaCl) (δ = −
533.6 ppm (relative to pure VOCl ₃ ); value is VOC at δ = 0 ppm
(values for 1 ₃ ) and ¹⁸³ W are 2.0 M Na ₂ W
It was O ₄ .2H ₂ O (WO ₄ ²⁻ (aq), δ = 0 ppm). The spectral parameters for ²⁷ Al were as follows: Sweep width 13500 Hz (wide window)
Or 2350 Hz (narrow window used for exact integration); pulse width 18 microseconds;
Delay 10 microseconds. ²⁷ Al resulting from Al (III) ions in glass sample tubes
To minimize signal intensity changes, all spectra were obtained from NMR tubes of the same quality and composition obtained from a single manufacturer: Wilmad grade 528-pp.
(Manufactured by Wilmad Glass, Buena, NJ). The NMR software package NUTS (1-D version, Acorn NMR, Inc., Fremont, Calif.) Was used to correct the “rolling” at the baseline of the ¹⁸³ W NMR spectrum.

B) Delignification of Wood Pulp According to a further aspect of the invention there is provided a method of using a derivative of tungstoaluminate of the type described above (mixed additive) as delignification and bleaching agent.

For example, according to the present invention, a substance such as wood pulp, xylem fiber, lignocellulosic fiber and lignocellulosic pulp is contacted with a polyoxometallate complex solution represented by the above general formula to obtain A method of delignifying a substance,
The pH of the solution is adjusted to 1 to 11, the consistency of the mixture of polyoxometallate and fiber or pulp is about 1 to 20%, and the mixture is mixed in a temperature-controlled and pressure-controlled container in a polyoxometalate. Methods are provided for heating under temperature and time conditions in which the metallate is reduced and enhanced delignification occurs. Methods for delignifying wood pulp and other lignocellulosic pulps with polyoxometallates are described in US Pat. Nos. 5,695,605, 5,302,248 and 5,5.
No. 552,019. These patents are incorporated herein by reference.

According to a preferred embodiment of the present invention, the pH of the solution is in the range 6-11. Preferably, the pH of the solution is in the range 6-9.

Preferably, the reduced polyoxometallate complex is treated with an oxidant selected from the group consisting of air, oxygen, hydrogen peroxide, other organic or inorganic peroxides (free acid or salt form) and ozone. Reoxidize with. The preferred oxidant is oxygen.

According to yet another aspect of the present invention, there is provided a method for wet-oxidizing a soluble organic lignin or a polysaccharide fragment or an oxidation product using the polyoxometallate complex represented by the above general formula. In the present method, a step of heating a solution containing both a polyoxometallate and an organic fragment or a product in the presence of an oxidizing agent under the conditions of oxidative decomposition of a dissolved organic compound to form a volatile organic compound and water. including. Preferably, this reaction is carried out in a pressure and temperature controlled vessel. Preferably, the reaction is conducted under conditions of pressure of 10 to 2,000 psi (0.069 to 13.79 MPa) and ambient temperature to 500 ° C. The pH is 0 to 11, preferably 6 to
It is preferably 9. The oxidant is preferably selected from air, oxygen, hydrogen peroxide, other organic or inorganic peroxides (free acid or salt form) and ozone. The oxidant is most preferably oxygen. The following Examples IC, III and IV illustrate this aspect of the invention.

Polyoxometalate delignification of wood pulp or other lignocellulosic pulp or a process for oxidative degradation of lignin and polysaccharide fragments dissolved during bleaching is described.
It is disclosed in US Pat. No. 5,549,789, which is hereby incorporated by reference.

[0035]

【Example】

I. Preparation and characterization of K ₇ [AlVW ₁₁ O ₄₀ ] and related compounds. Preparation of H ₅ [AlW ₁₂ O ₄₀ ] (mixture of α and β isomers). Step 1: 11 [WO ₄ ] ^2- + 2Al ³⁺ + 10H ⁺ → [Al (Al)
W ₁₁ O ₃₉ ] ⁶⁻ + 5H ₂ O Step ₂ : ₁₂ [Al (Al) W ₁₁ O ₃₉ ] ⁶⁻ + 56H ⁺ → 11 [AlW ₁₂
O ₄₀ ] ^5- + 13Al ³⁺ + 28H ₂ O

[0036]   Step 1: Sodium tungstate dihydrate (NaWO_Four・ 2H₂O, 100g
, 0.304 mol), add a magnetic stir bar and remove the addition funnel and condenser.
In a 1,000 mL three-necked round bottom flask equipped with₂Dissolved in 400 mL of O
It was Hydrochloric acid (HCl, 23.0 mL, 0.276 mol) was stirred vigorously in this solution.
Dropped with a pipette while stirring. Slowly add acid over 20-30 minutes
This largely, if not completely, avoids the precipitation of tungstic acid. at this point
The pH of the solution should be about 7.7 (it is important for the pH to exceed 7.0).
Important). The solution is heated to the reflux point and aluminum chloride hexahydrate (AlCl ₃ ・ 6H₂O, 13.32 g, 0.0552 mol) dissolved in 80 mL of water
Through a dropping funnel over about 90 minutes (about 5-6 drops / minute) with constant stirring.
It was dripped. During the addition, the solution becomes slightly cloudy. However, allow the addition enough
It must be done rapidly to avoid excessive precipitation. Only
However, if this occurs, stop the addition and add solution until clearer.
Must be stirred. All AlCl₃After adding, the solution is temporarily refluxed.
Hold, cool to room temperature and filter through a medium sintered glass frit. The final pH is
Should be about 7.

[0037]   Step 2: Na at this point₆[Al (Al) W₁₁O₃₉] (²⁷AlNMR: 73p
pm, Δv_1/2= 89 Hz; 8 ppm, Δv_1/2= 256 Hz; including Figure 1)
The above solution was transferred to a 1,000 mL round bottom flask equipped with a reflux condenser.
. Carefully add concentrated sulfuric acid (about 20 mL, 0.376 mol) to the solution.
Was acidified to pH 0. After the pH reached 0, add 3 mL of concentrated sulfuric acid,
The solution was heated to reflux. Initial cloudiness or yellow color should disappear within 16 hours
No The solution was kept at reflux for 6 days to ensure complete conversion to product.
Must have. Then, after cooling to room temperature, the solution is poured into a medium glass frit.
May be filtered (if cloudy is visible). H at this point_Five[AlW_{1 2} O₄₀], H⁺, Na⁺, Al³⁺, Cl^-And SO_Four ^2-A solution containing
Transferred to a 0 mL beaker and cooled to 0 ° C.

Cold (−20 ° C.) concentrated sulfuric acid (147 mL) is added carefully to avoid excessive heating. The solution was then cooled again to 0 ° C. and transferred to a 2,000 mL separatory funnel.
Diethyl ether (500 mL) was added and the mixture was shaken very gently with frequent aeration until rapid evaporation of diethyl ether subsided. The mixture was then shaken more vigorously, still with frequent ventilation, and allowed to stand until the three layers separated. The top colorless transparent layer is diethyl ether, the middle slightly cloudy layer is the aqueous phase, and the bottom layer (dense pale yellow viscous liquid) is H ₅ [Al.
W ₁₂ O ₄₀ ] (α isomer and β isomer). The bottom (ethereal) layer (approximately 20 mL total) was collected in a 50 mL beaker, gently heated (4-5 hours) in a warm water bath and concentrated to dryness. The crude product (69.2 g, 95%) was recrystallized by dissolving it in 20 mL of hot water, concentrating to a volume of 23 mL by gentle heating and then cooling at 0 ° C. for 16 hours. Yield: 50.46 g, 64%. IR
(KBr pellet): 972, 899, 795 (broad), 747 (broad), 538 and 477 cm ^-1 . Analysis result: Calculated value (measured value) for H ₅ [AlW ₁₂ O ₄₀ ] · 15H ₂ O: H1.12 (1.15) W70.07 (70.23) A
10.86 (0.89). White crystals α- [AlW ₁₂ O ₄₀ ] ^5- and pale yellow β- [A
lW ₁₂ O _40] ^5- (the amorphous and more soluble), can be separated by fractional crystallization. α-
The ²⁷ Al and ¹⁸³ W NMR spectra of [AlW ₁₂ O ₄₀ ] ⁵⁻ and β- [AlW ₁₂ O ₄₀ ] ⁵⁻ are shown in FIGS. 2A and 2B.

B. Preparation of α-Na ₅ [AlW ₁₂ O ₄₀ ]. A 65.9 g sample of Na ₅ [AlW ₁₂ O ₄₀ ] (mixture of α and β isomers) was dissolved in 130 mL of water. P of solution
H was adjusted to about 6 with 0.75M Na ₂ CO ₃ (15.0 mL). The solution was heated to reflux for 3 days: by ²⁷ Al NMR spectrum, 72.1 pp
resonance at m (alpha isomer) accounted for about _{95% [AlW 12 O 40]} 5- of the solution.
After cooling to room temperature, the solution was concentrated by rotary evaporation until precipitation started to form and cooled to 5 ° C in the refrigerator. The product was collected on a coarse glass frit and air dried. Yield: 32.24 g (48.9%). ¹⁸³ W NMR, δ: -107.5 ppm. ²⁷
Al NMR, δ: 72.1 ppm (Δv _1/2 = 0.93 Hz). IR (KBr
Pellets): 955, 883, 799, 758, 534 and 498 cm ^-1 . Analysis result: Calculated value (measured value) for Na ₅ [AlW ₁₂ O ₄₀ ] .13H ₂ O: H0.
81 (0.78) W68.47 (68.22) Al0.84 (0.88), Na
3.57 (3.39).

[0040]   C. H at high pH_Five[AlW₁₂O₄₀] Stability. At pH 5 [SiW₁₂O₄₀]^{Four -} Rapidly hydrolyzes at room temperature [SiW₁₁O₃₉]^8-Very different from the stability of
The data for Example IB is [AlW₁₂O₄₀]^Five-However, under the conditions of pH 6 and 100 ° C,
It is stable for at least 3 days.

D. Isolation of β-Na ₅ [AlW ₁₂ O ₄₀ ]. Crude H ₅ [AlW ₁₂ O ₄₀ ] (100 g
, 0.0321 mol) in 60 mL of water and filtered through a medium frit. 0
． The acid was neutralized to a final pH of 2.4 by pipetting a solution of 75M Na ₂ CO ₃ (116 mL, 0.087 mol). The solution was concentrated in vacuo until a precipitate began to form and cooled to 5 ° C. The product was collected on a medium glass frit and air dried. The first crop (7.15 g) judged to be an impurity by IR spectroscopy was discarded. The second crop (40.02 g, 39%) was mostly β- [AlW ₁₂ O ₄₀ ] ⁵⁻ (90% β ²⁷ Al NMR, 10% α isomer). IR (KBr pellet): 966 (m), 893 (m), 799 (s)
, 757 (s), 545 (w) and 481 (w) cm ^-1 . Analysis result: Na ₅ [A
Calculated value (measured value) for 1W ₁₂ O ₄₀ ] · 13H ₂ O: H0.81 (0.77
) W68.47 (68.25) Al0.84 (0.87) Na3.57 (3.4
0).

E. Preparation of α-K ₅ [AlW ₁₂ O ₄₀ ]. A 5.0 g sample of H ₅ [AlW ₁₂ O ₄₀ ] (mixture of α isomer and β isomer) was dissolved in 5 mL of water, and 10 mL of saturated KCl solution was dissolved.
Was added. The solution was placed in a vial, stoppered and stored in the dark at room temperature for several weeks. Colorless crystals of the K ⁺ salt of the α isomer (less soluble) formed slowly. One of the crystals was used for X-ray crystallography. Analysis result: K ₅ [AlW ₁₂ O ₄₀ ]
· 19H ₂ O Calculated for (Found): H1.12 (1.07) W64.6
8 (64.76) Al0.79 (0.78) K5.73 (5.68).

F. Crystal data for α-K ₅ [AlW ₁₂ O ₄₀ ] .17H ₂ O. Colorless crystals:
Dimensions 0.31 x 0.24 x 0.21 mm, hexahedron P6 ₂ 22 (a = 19.07)
20 (1) Å, c = 12.5658Å, V = 3958.34 (7) Å ³ , dc =
4.223 g cm ^-3 , Z = 3). A total of 25,389 reflections of MoKα rays (λ =
0.71073 Å) using the Siemens SMART system,
Corrected for absorption. Of these, 3274 exceeded 4σ (F). The structure was solved by a direct method, and the oxygen atoms of Al1, O1, O2, O3 and water of crystallization were purified isotropically. It was purified by full matrix minimum-squares-on-F ² method by. K (3) and K (4 during final purification
), The partial occupancy and the common anisotropy parameter were used. In final convergence,
For the 143 parameters, R ₁ (I> 2σI) = 3.42%, R ₂ = 7.45%
And GOF = 1.02. Related bond length (Å): Al (1) -O (3),
1.742 (8); W (1) -O (1), 1.910 (8); W (1) -O (2
), 1.909 (8); W (1) -O (3), 2.265 (8); W (1) -O
(4), 1.704 (8); W (1) -O (6), 1.976 (8); W (2)
-O (2), 1.935 (8); W (2) -O (5), 1.961 (8); W (
2) -O (7), 1.710 (9); W (2) -O (8), 1.896 (9);
W (2) -O (9), 1.901 (9); W (3) -O (10), 1.704 (
8); W (3) -O (1), 1.899 (8); W (3) -O (9), 1.96.
4 (8). The structure (polyhedral notation) is shown in FIG.

G. Preparation of α-K ₉ [AlW ₁₁ O ₃₉ ]. Sample 43.76 of H ₅ [AlW ₁₂ O ₄₀ ].
g (14.1 mmol; mixture of α and β isomers) was dissolved in 100 mL of water and heated to 60 ° C. in a beaker equipped with a variable temperature pH meter.
With constant stirring, 6.97 g of solid K ₂ CO ₃ .1.5H ₂ O (42.3 mmol, 3 eq) was added slowly. Foam (formation of CO ₂₎ was observed, slowly carried addition, the reaction mixture was not allowed to overflow from the beaker. Next, 11.62 g (70.5 mmol, 5 equivalents) of K ₂ CO ₃ .1.5H ₂ O
To 20 mL of water was added dropwise, being careful to keep the pH below 8 until at least 75% of the carbonate solution was added. During the course of the addition, the product, a white powder, began to precipitate. During the last 25% addition of carbonate solution,
The pH was increased to 8.5. Final pH values typically ranged from 8 to 8.25. Then the mixture was cooled to 5 ° C. for several hours. Precipitate α-K ₉ [AlW ₁₁ O ₃₉
] (White powder) was collected on a medium porosity glass frit, washed 3 times with 20 mL each of water and air dried. Yield: 41.8 g (92%, 100% α isomer based on ²⁷ Al, ⁵¹ V and ¹⁸³ W NMR spectrum standards of K ₅ [AlW ₁₂ O ₄₀ ] and K ₅ [AlVW ₁₁ O ₄₀ ] derivatives). Reprecipitation is not practical because α-K ₉ [AlW ₁₁ O ₃₉ ] is only slightly soluble in water (2 g in 100 mL at 22 ° C.). ²⁷ Al NMR,
δ: 63.3 ppm (Δv _1/2 = 1735 Hz). IR (KBr pellet) 93
7, 868, 789, 756 (shoulder), 704, 524 and 493 cm ^-1 . Analysis result: Calculated value (measured value) for K ₉ [AlW ₁₁ O ₃₉ ] .13H ₂ O: H
0.80 (0.77) W62.05 (61.87) Al0.83 (0.78) K
10.80 (10.92).

[0045]   H. α-K₆[Al (Al^IIIOH₂) W₁₁O₃₉] Preparation of α-K₉[AlW₁₁O ₃₉ 5.18 g (1.58 mmol) of the sample] was added to 15 mL of water and stirred to form a salt.
Aluminum chloride hexahydrate (AlCl₃・ 6H₂O, 0.38 g, 1.5 mmol)
Was dissolved in 5 mL of water, and the solution was quickly added by a pipette. 15 minutes at room temperature
After stirring, the mixture was stirred in a warm water (60 ° C) bath until the solution became clear (about 5
Minutes). The final pH of the solution was 6.7. The solution is cooled to room temperature and neutralized.
Filter through a lath frit and cool to 5 ° C. until crystals form. Collect crystals,
Dried on coarse frit. Yield: 3.77 g (75%).¹⁸³W NMR (
FIG. 6C), δ (integral): −60.7 (2), −103.2 (2), −132.0.
(1), -142.9 (2), -152.0 (2), -205.1 (2).²⁷A
l NMR, δ: 74.3 (Δv_1/2= 78.5 Hz) and 8.8 ppm (Δv_{1 / 2} = 205.5 Hz). IR (KBr pellet): 948 (m), 876 (s)
, 799 (s), 765 (m), 735 (sh), 685 (w), 531 (w)
And 497 (w) cm^-1. Analysis result: K₆[Al (AlOH₂) W₁₁O₃₉] ・ 15
H₂Calculated value for O (actually measured value): H 0.94 (0.87) W 63.10 (6
2.80) Al 1.68 (1.62) K7.32 (7.04).

[0046]   I. K₇[AlV^IVW₁₁O₄₀] Preparation of Vanadyl sulfate trihydrate (VOSO_Four・ 3
H₂O) 0.39 g (1.80 mmol) was added to 5 mL of water to prepare a solution.
, K₉[AlW₁₁O₃₉] 5.43 g (1.80 mmol) in 10 mL of deionized water
The slurry added to was added quickly by pipette. Mixture immediately dark purple
Became. The solution was stirred for 10 minutes and filtered through a medium glass frit. Number of filtrates
After cooling at 5 ° C. for an hour, dark purple crystals were collected, dried on a medium frit and washed with a minimum amount of warm water (
It was recrystallized at 60 ° C. Yield: 3.5 g (61%). IR (KBr pellet):
942 (m), 871 (m), 793 (s), 761 (m), 697 (w), 5
37 (w), 492 (w) and 473 (w) cm^-1. Analysis result: K₇[AlVW_{1 1} O₄₀] ・ 13H₂Calculated value for O (actual measured value): H0.81 (0.76) W6
2.26 (62.23) Al0.83 (0.69) V1.57 (1.71) K8
． 43 (8.34). In solution, [AlVW₁₁O₄₀]^7-V (IV) at
The ions were paramagnetic and no NMR signal was observed. However, Bana
The element is bromine element (Br₂), It is easily oxidized in the solution.
Becomes diamagnetic V (V). Next, [AlVW₁₁O₄₀]^6-About the spectrum
I can guess.¹⁸³W NMR, delta (integration): -83.1 (2), -99.1 (2).
, -119.5 (2), -123.0 (1), -124.0 (2) and -144.
． 4 (2) ppm.²⁷Al NMR, δ: 72.5 ppm (Δv_1/2= 175H
z).⁵¹V NMR, δ: −535.5 ppm (Δv_1/2= 220 Hz).

J. Preparation of α-K ₅ [AlV ^V W ₁₁ O ₄₀ ]. VOSO ₄ .3H ₂ O (12.20 mL of 0.5 M solution, 6.1 mmol) was added to K ₉ [AlW ₁₁ O ₃₉ ] (20 g, 6.1).
Millimoles) was added dropwise to a slurry prepared by adding 50 mL of water and K ₇ [AlV ^IV
A purple solution of W ₁₁ O ₄₀ ] (about 0.1 M) was obtained. 2 eq HCl (4 mL of 3M solution
) Was added to the solution to consume the hydroxide generated by the subsequent oxidation of V (IV) to V (V) by reaction with ozone. A stream of ozone was then bubbled through the solution until the color changed to light yellow. Then oxygen was bubbled through the solution for a few minutes to remove unreacted ozone and the solution was rotary evaporated to half its initial volume.
After cooling overnight at 5 ° C., yellow crystals α-K ₆ [AlVW ₁₁ O ₄₀ ] were collected on a medium frit, air dried and recrystallized with a minimum amount of hot water (80 ° C.). Yield: 12.95g (
66%). IR (KBr pellet): 950 (m), 878 (s), 794 (s
), 756 (s), 542 (w) and 487 (w) cm ⁻¹ . Analysis result: K ₆ [A
LVW ₁₁ O ₄₀ ] · 13H ₂ O calculated value (measured value): H0.82 (0.7
8) W63.02 (62.97) Al0.84 (0.88) V1.59 (1.8
8) K7.31 (7.29). ²⁷ Al NMR, δ: 72.5 ppm (Δv _1/2
= 175 Hz, FIG. 4). ⁵¹ V NMR, δ: −535.5 ppm (Δv _1/2 = 2
20 Hz, FIG. 5). ¹⁸³ W NMR (FIG. 6B), δ (integration): −83.1 (2).
, -99.1 (2), -119.5 (2), -123.0 (1), -124.0.
(2), -144.4 (2) ppm.

K. Preparation of α-K ₈ [Al (Mn ^II OH) W ₁₁ O ₃₉ ]. K ₉ [AlW ₁₁ O ₃₉ ] (
10.0 g of a sample (3.05 mmol) was added to 100 mL of water and stirred. Manganese sulfate hydrate (MnSO ₄ .H ₂ O, 0.516 g, 3.05 mmol) was dissolved in 10 mL of water and then rapidly added to the K ₉ [AlW ₁₁ O ₃₉ ] slurry with a pipette. The resulting mixture was stirred at 80 ° C. for about 10 minutes in a water bath until all solids dissolved to form a golden solution. The final pH of the solution was 6.3. After cooling to room temperature, the solution was filtered and then refrigerated overnight. The product, a brownish-yellow amorphous powder, was collected and dried on a crude frit. Yield: 8.5 g (85.7%). The product was recrystallized with a minimum amount of warm water. IR (KBr pellet): 933 (m), 871
(M), 796 (s), 766 (sh), 698 (m), 526 (w) and 48
6 (w) cm ^-1 . Analysis result: Calculated value (measured value) for K ₇ [AlMnW ₁₁ O ₃₉ ] .13H ₂ O: H0.81 (0.79) W62.49 (62.34) Al0.3.
83 (0.96) Mn 1.70 (1.44) K8.46 (8.20).

L. Preparation of α-K ₆ [Al (Mn ^III OH ₂ ) W ₁₁ O ₃₉ ]. K ₉ [AlW ₁₁ O ₃₉ ]
20 g of (6.1 mmol) was added to 100 mL of water and stirred. Mn
A solution of SO ₄ .H ₂ O (1.03 g in 10 mL of water) was added dropwise to the resulting slurry with a pipette. The reaction mixture was added to a hot water bath (70-80 ° C) and stirred for about 10 minutes until the solution became clear. The pH of the solution was lowered to about 3 with 1M HCl solution and the household bleach (Blue Ribbon ™, NaOCl5) was added.
． A 25% solution of 4.33 g of bleach (approximately half diluted with water) was added while monitoring the pH. When about 75% bleach was added, the pH rose to 5.3 and did not decrease. Therefore, a few more drops of 1M HCl were added to bring the pH back to about 3. During the process of adding the bleach, the color of the solution changed from gold yellow to deep pink purple. The solution was concentrated in vacuo until a precipitate began to form and refrigerated at 5 ° C overnight. The pink purple precipitate was collected on a crude glass frit, vacuum dried and recrystallized with a minimum amount of warm water. Yield: 12.4
5 g (63%).

M. Preparation of α-K ₈ [Al (Co ^II OH) W ₁₁ O ₃₉ ]. K ₈ [Al except that Co (NO ₃ ) ₂ .6H ₂ O (0.888 g) was used instead of MnSO ₄ .H ₂ O
The same operation as the preparation of (Mn ^II OH) W ₁₁ O ₃₉ ] was repeated (pH after addition was 6
． 2). The resulting solution (after heating in a water bath) was dark pink and the product was a red powder. Yield: (2 yields) 7.31 g (74%). Two yields,
Recrystallized together with a minimum amount of warm water (60 ° C.). Recrystallized product yield: 3.66 g (37
%). IR (KBr pellet): 952 (m), 935 (s), 891 (s),
798 (m), 697 (m), 533 (w) and 486 (w) cm ^-1 . Analysis result: Calculated value (measured value) for K ₇ [AlCoW ₁₁ O ₃₉ ] · 15H ₂ O: H0.9
2 (0.91) W61.73 (62.26) Al0.82 (0.88) Co1.
80 (1.73) K 8.35 (8.16).

N. Preparation of α-K ₆ [Al (Co ^III OH ₂ ) W ₁₁ O ₃₉ ]. K ₉ [AlW ₁₁ O ₃₉ ]
20 g of (6.1 mmol) was added to 100 mL of water and stirred. Co
The _{(NO 3) 2 · 6H 2} O in solution (in water 10 mL 2.15 g), was added dropwise by pipette to the resulting slurry. The reaction mixture was added to a hot water bath (70-80 ° C) and stirred for about 10 minutes until the solution became clear. After cooling to room temperature, the solution is filtered and
Acidified to pH 2 with 4.0 mL M HCl. A stream of ozone was passed through the solution until it turned dark green. The solution was concentrated in vacuo until a precipitate began to form and refrigerated at 5 ° C overnight. The crystalline product was collected on a crude glass frit, vacuum dried and recrystallized with a minimum amount of warm water. Yield: 11.33 g (58%). ¹⁸³ W NMR, δ (integration): +
148.5 (2), -60.3 (2), -89.7 (2), -120.6 (1)
, -146.6 (2) and -149.0 (2) ppm (Fig. 6A). ²⁷ Al NM
R, δ: 74.7 ppm.

II. The [AlVW ₁₁ O _40] ^6- bleaching delignified of [AlVW ₁₁ O _40] ^6- by wood pulp, indicated by the number sets of conditions. The microkappa number (TAPPI UM246) of the bleached pulp was determined by FT-Raman spectroscopy, and the viscosity was determined by the capillary viscosity method (TAPPI T230 o.
m-89).

The first experimental condition was that 0.05 M [AlVW ₁₁ O ₄₀ ] ^{6 −} was added to 0.3 M acetate buffer at 125 ° C. for 1 hour at a pulp consistency of 0.5%. The starting kappa number of the pulp was 31.8 and the final kappa number was 17.0.

The second experimental condition was to add 0.1 M [AlVW ₁₁ O ₄₀ ] ^{6 −} to 0.1 M sodium tungstate (pH adjusted to 7.5 to 7.6) at 125 ° C. for 10 hours. , Pulp consistency 1% or 2%, initial kappa number 31.8 and viscosity 31.
It was 4 mPa · s. The three samples treated at 1% consistency had Kappa numbers of 15.0, 16.4 and 17.8 after bleaching and washing, respectively. The viscosity of the sample having a kappa number of 15.0 was 22.5 mPa · s. 2% consistency
The two samples in Table 1 had Kappa numbers of 22.0 and 27.7, respectively. Kappa value 2
The viscosity of the pulp of 2.0 was 18.0 mPa · S. The [AlVW ₁₁ O ₄₀ ] ^6- solution was dark brown after delignification and was reduced by lignin during the reaction.
It can be seen that VW ₁₁ O ₄₀ ] ⁷⁻ exists.

[0055] III. With oxygen [AlVW₁₁O₄₀]^7-Oxidation of [AlVW₁₁O₄₀]^6-The useful property of is that the reduction potential is such that the reduced form of the anion [Al
VW₁₁O₄₀]^7-Is oxygen (O₂) Is sufficiently negative to be easily oxidized by
Is. 0.001M [AlVW₁₁O₄₀]^7-0.01M sodium tungstate
A solution (pH adjusted to 7) prepared by adding it to um dihydrate was purged with oxygen (O. ₂ (By bubbling through the solution for 3 minutes) and gas sealing with an oxygen layer,
It was sealed in a Teflon liner inside a stainless steel pressure vessel. 9 at 200 ° C
After heating for 0 minutes, it was taken out of the pressure vessel. The solution, which was initially dark purple, is bright yellow
It became a color, and the reducing anion [AlVW] that was initially present₁₁O₄₀]^7-(Purple) is [A
LVW₁₁O₄₀]^6-It can be seen that it was oxidized to (yellow). No precipitation observed
It was The degree of oxidation was quantified by UV-Visible spectroscopy (540 nm). [Al
VW₁₁O₄₀]^7-At least 95% of the [AlVW₁₁O₄₀]^6-Was oxidized to.

[0056] IV. [AlVW₁₁O₄₀]^6-Wet oxidation (mineralization) using oxygen and oxygen   [AlVW₁₁O₄₀]^6-The reduction potential of [PV₂Mo_TenO₄₀]^Five-Same as the reduction potential of
Like (excellent wet oxidation catalyst⁸(Fig. 7)). [PV in wet oxidation₂Mo_TenO ₄₀ ]^Five-The role of a catalyst in Fc facilitates the transfer of electrons from dissolved organic compounds to oxygen
Therefore, the reduction potential (the ease with which the anion accepts and discards an electron) is
It is an important determinant. Reduction potential is a thermodynamic parameter. Reducing anion
The reaction rate of is also important for determining its effectiveness as a wet oxidation catalyst. [A
LVW₁₁O₄₀]^6-The reduction potential of [PV₂Mo_TenO₄₀]^Five-Similar to the reduction potential of
(Fig. 7), [AlVW₁₁O₄₀]^7-Is O₂By [AlVW₁₁O₄₀]^6-
Is rapidly oxidized to [AlVW₁₁O₄₀]^6-And [AlVW₁₁O₄₀]^6-Melting
The liquid or a combination thereof is used for wet oxidation of dissolved lignin and polysaccharide fragments.
It will act effectively as a catalyst.

V. [AlMn ^II W ₁₁ O ₄₀ ] ⁷⁻ and [AlCo ^II W ₁₁ O ₄₀ ] ⁷⁻ are each [Al
Oxidation of Mn ^III W ₁₁ O ₄₀ ] ^6- and [AlCo ^III W ₁₁ O ₄₀ ] ^6- by ozone

These reactions were carried out according to the procedure described in Example I. As described in detail in L, by bubbling O ₃ (in O ₂ ) through a solution of [AlMn ^II W ₁₁ O ₄₀ ] ^7- or [AlCo ^II W ₁₁ O ₄₀ ] ^7- . .

[Brief description of drawings]

FIG. 1a shows Example I. Na ₆ [Al ₂ W ₁₁ O ₃₉ ] prepared as described in A.
²⁷ is a ²⁷ Al NMR spectrum of (a mixture of α isomer and β isomer). Figure 1b
In Example I. 18A is a ¹⁸³ W NMR spectrum of Na ₆ [Al ₂ W ₁₁ O ₃₉ ] (mixture of α isomer and β isomer) prepared as described in A. FIG.

2A and 2B show α-H ₅ [AlW ₁₂ O ₄₀ ] ^5- (left side) and β-H ₅ [Al.
²⁷ Al and ¹⁸³ W NMR spectra and structure (polyhedral notation) of W ₁₂ O ₄₀ ] ^5- (right side) are shown. FIG. 2C contains α-H ₅ [Al ^III W ₁₂ O ₄₀ ] and β-H ₅ [Al ^III W ₁₂ O ₄₀ ] (see inset) and [Al (H ₂ O) ₆ ] ³⁻ . ²⁷ A of reaction mixture
2A to 2C are ²⁷ Al atoms (abundance 10%).
0%: I = 5/2) is a tetrahedral site (α- [AlW ₁₂ O ₄₀ ] ^5- , Δv _1/2 = 0 located at the center of W ^VI ₁₂ O ₄₀ ^8- shell of WO ₆ octahedron. 2.9 Hz, ²⁷ Al NMR signal) or pseudo-tetrahedral site (β- [AlW ₁₂ O ₄₀ ] ^5- , Δv _1/2 = 5.1 Hz
) Occupy.

FIG. 3 is a structure (polyhedral notation) of α- [AlW ₁₂ O ₄₀ ] ⁵ -determined by X-ray crystallography.

FIG. 4 shows a ²⁷ Al NMR spectrum of α- [AlVW ₁₁ O ₄₀ ] ^6- .

FIG. 5 shows a ⁵¹ V NMR spectrum of α- [AlVW ₁₁ O ₄₀ ] ^6- .

FIG. 6a shows a ¹⁸³ W NMR spectrum of α- [Al (Co ^II OH ₂ ) W ₁₁ O ₃₉ ] ^6- . FIG. 6b shows the ¹⁸³ W NMR spectrum of α- [AlVW ₁₁ O ₄₀ ] ^6- . FIG. 6c shows the ¹⁸³ W NMR spectrum of α- [Al (AlOH ₂ ) W ₁₁ O ₃₉ ] ^6- .

FIG. 7: [PV ₂ Mo ₁₀ O ₄₀ ] ^5- (pH 4) electrolyte aqueous solution, [SiVW ₁₁ O ₄₀ ] ^5- electrolyte aqueous solution, [AlVW ₁₁ O ₄₀ ] ^6- electrolyte aqueous solution, and dioxygen (O ₂ ) Reduction potential (volt vs. standard hydrogen reference electrode, NHE) vs. pH and the approximate stability range of the POM anion is indicated by the horizontal line.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, SD, SZ, UG, ZW), EA (AM , AZ, BY, KG, KZ, MD, RU, TJ, TM) , AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CZ, DE, DK, E E, ES, FI, GB, GE, GH, GM, HR, HU , ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, M D, MG, MK, MN, MW, MX, NO, NZ, PL , PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, V N, YU, ZW (72) Inventor Wayne Stock, Iraei             United States Georgia 30329,             Atlanta, Bria Vista Way             144 (72) Inventor Carwan, Jennifer Jay             30033, Georgia, USA             Decayer, Valley Brooke Crow             Singing 330 (72) Inventor Liner, Richard S             Wisconsin, United States             53704, Madison, Dwight Drive               4406, apartment 4 (72) Inventor Hill, Craig El             United States Georgia 30345,             Atlanta, Cravie Drive             2941 F term (reference) 4L055 AD07 AD08 AD09 AD10 AD11                       AD17 BB17 BB18 BB19 BB20                       BB21 EA25 EA29 EA31 FA22                       FA30

Claims (15)

[Claims] 1. A method for delignification of lignocellulosic fibers, comprising: a) a formula [Al ₁ V _{m Mn} W _o Nb _p Ta _q (TM) _r O _s ] ^x- (where l is 1 to 1). 6, m is 0 to 18, n is 0 to 40, o is 0 to 40, and p is 0.
-10, q is 0-10, r is 0-9, TM is a d-electron-containing transition metal ion (provided that l + m + n + o + p + q ≧ 4), and s is sufficient to satisfy x> 0. A large number) and a polyoxometallate complex having an aluminum heteroatom represented by a lignocellulosic fiber formulation, wherein the resulting formulation has a pH of 6-11 and a consistency of 1- 20%; and b) heating the resulting formulation in a temperature and pressure controlled vessel under conditions of temperature and time at which polyoxometallate is reduced and delignification occurs. How to be. 2. The polyoxometallate is [Al_lV_m(TM)_nW_oO_p]^{x -} (In the formula, 1 is 1 to 2, m is 0 to 6, n is 0 to 3, and o is 0 to
12 and TM is a d-electron-containing transition metal ion (provided that 1 + m + n + o =
12 or 13), p is a number large enough to satisfy x> 0),
The method according to Item 1. 3. The polyoxometallate is [AlVW ₁₁ O ₄₀ ] ^6- .
The method of claim 1. 4. The method according to claim 1, wherein the pH is 6-9. 5. The lignocellulosic material is a lignocellulosic pulp,
The method according to claim 1, which is at least one of wood fiber and wood pulp. 6. The method of claim 1, wherein the reduced polyoxometallate complex is reoxidized with an oxidant selected from the group consisting of air, oxygen, hydrogen peroxide, organic and ozone. 7. The method of claim 6, wherein the oxidant is oxygen. 8. The method according to claim 1, wherein the reduced polyoxometallate complex is reoxidized with an organic peroxide or an inorganic peroxide. 9. A method for the oxidative degradation of lignin and polysaccharide fragments dissolved during the polyoxometallate treatment of a lignocellulosic material, comprising the steps of: a) obtaining a lignocellulosic formulation; and b) said formulation. and wherein _{[Al l V m Mo n W} o Nb p Ta q (TM) r O s] x- ( wherein, l is 1 to 6, m is 0 to 18, n is 0 to 40 And o is 0 to 40
, P is 0 to 10, q is 0 to 10, r is 0 to 9, TM is a d-electron-containing transition metal ion (provided that 1 + m + n + o + p + q ≧ 4), and s is x> 0. A solution of a polyoxometallate represented by the formula (1) to a solution having a consistency of 1 to 20%, wherein the composition is delignified. And reducing the polyoxometallate to dissolve the lignin and the polysaccharide fragment in the formulation to obtain a liquid containing the polyoxometallate and the dissolved lignin and the polysaccharide fragment, c) Gaseous oxidation The liquid is heated in the presence of an agent to oxidize the polyoxometallate and volatilize the dissolved lignin and the polysaccharide fragment by the oxidand and the polyoxometallate. A method comprising the steps of causing oxidation under the conditions contact and oxidative degradation to objects and water, i) the pressure of said oxidizing agent in said heating step, 15～1,000Psia (
0.103-6.895 MPa in absolute pressure), ii) the temperature of the heating step is 100-400 ° C., iii) the heating step is carried out at a final pH of 1.0-11.0, iv ) The oxidation time is 0.5 to 10.0 hours, and v) the heating step is performed in a container capable of withstanding the pressure. 10. The polyoxometallate has the formula [Al_lV_m(TM)_nW_oO _p ]^x-(In the formula, 1 is 1 to 2, m is 0 to 6, n is 0 to 3, and o is
0 to 12, TM is a d-electron-containing transition metal ion (provided that 1 + m + n +
o = 12 or 13), and p is a number large enough to satisfy x> 0)
10. The method of claim 9, which is 11. The method according to claim 9, wherein the polyoxometallate is represented by the formula [AlVW ₁₁ O ₄₀ ] ^6- . 12. The method of claim 9, wherein the oxidant is oxygen. 13. The method of claim 9, wherein the lignocellulosic blend is at least one of lignocellulosic pulp, xylem fiber and wood pulp. 14. The method of claim 12, wherein the lignocellulosic formulation is xylem fiber. 15. The method of claim 12, wherein the lignocellulosic formulation is wood pulp.