KR20140001830A - Nickel compositions for preparing nickel metal and nickel complexes - Google Patents

Abstract

Nickel (II) compositions for use in making nickel metal (Ni (0)) compositions, and in particular, methods of making basic nickel carbonates for use in producing nickel metal compositions. By varying the molar ratio of carbonate and bicarbonate to nickel salt, the process provides a basic nickel carbonate that produces an excellent nickel metal containing solid suitable for forming nickel-ligand complexes with phosphorus containing ligands. The phosphorus containing ligand may be a mono or bidentate ligand.

Description

[0001] NICKEL COMPOSITIONS FOR PREPARING NICKEL METAL AND NICKEL COMPLEXES [0002]

Related application

This application claims the benefit of U.S. Provisional Application No. 61 / 287,757, filed December 18, 2009, U.S. Provisional Application No. 61 / 380,445, filed September 7, 2010, and PCT / Priority is claimed with the filing date of US2010 / 060388, each of which is incorporated herein by reference in its entirety.

Field of invention

The present invention relates to a nickel (II) composition for use in making a nickel metal (Ni (0)) composition, and in particular to a method of making a basic nickel carbonate (BNC) used to produce nickel metal compositions. Nickel metal compositions can be used to prepare a zero valent nickel catalyst complex with a phosphorus containing ligand.

Hydrocyanation catalyst systems for the hydrocyanation of ethylenically unsaturated compounds are known in the art. For example, a system useful for the hydrocyanation of 1,3-butadiene (BD) to form pentenitrile (PN) and a system for subsequent hydrocyanation of pentenitrile to form adiponitrile (ADN) Are known in the art of nylon synthesis.

Hydrogenation of ethylenically unsaturated compounds using transition metal complexes with monodentate phosphite ligands is described in the prior art. See, for example, U.S. Patent Nos. 3,496,215; 3,631,191; 3,655,723 and 3,766,237, and Tolman et al., Advances in Catalysis , 1985 , 33 , 1]. Hydrogenation of an activated ethylenically unsaturated compound such as a conjugated ethylenically unsaturated compound (e.g., BD and styrene) and a strained ethylenically unsaturated compound (e.g., norbornene) , Whereas the hydrocyanation of inactivated ethylenically unsaturated compounds such as 1-octene and 3-pentenenitrile (3PN) requires the use of a Lewis acid promoter. Recently, catalyst compositions and methods have been described for the hydrocyanation of monoethylenically unsaturated compounds using zero-valent nickel and bidentate phosphite ligands in the presence of a Lewis acid promoter; See, for example, U.S. Patent No. 5,512,696; 5,723,641 and 6,171,996.

U.S. Patent No. 3.90312 million and Ni (MZ _{3) 4} and Ni (MZ _{3) 2} A 0, the type of technology for producing a nickel complex; Wherein M is P, As or Sb; Z is R or OR - wherein R is an alkyl or aryl radical having up to 18 carbon atoms and can be the same or different and one or more Z is OR; A is a monoolefin-based compound having 2 to 20 carbon atoms; The R radical of a given MZ ₃ of Ni (MZ ₃ ) ₂ A is preferably chosen such that the cone angle of the ligand is at least 130 °; The nickel complex is prepared by reacting elemental nickel with a monomolecular MZ ₃ ligand in the presence of a halogen-containing derivative of a monodentate MZ ₃ ligand as a catalyst at a temperature ranging from 0 ° C to 150 ° C. A more rapid reaction is achieved by carrying out the preparation in an organic nitrile solvent.

In addition, U.S. Patent No. 4,416,825 discloses a process for preparing a zirconium compound having a monovalent organic phosphorus compound (ligand) by controlling the temperature of the reaction with respect to the amount of monodentate ligand and performing the reaction in the presence of a chlorine ion and an organic nitrile such as adiponitrile ≪ / RTI > describes an improved continuous process for preparing the hydrocyanation catalyst comprising the complexes.

There are several methods that can be used to prepare nickel catalyst complexes with phosphorus containing ligands. One method is the reaction between nickel bis (1,5-cyclooctadiene) [Ni (COD) ₂ ] and phosphite ligands; This method is not very economical due to the high cost of Ni (COD) ₂ . Another method involves the in situ reduction of anhydrous nickel chloride with zinc dust in the presence of phosphite ligands. For this reaction to be successful, the nickel metal must react with the phosphorus containing ligand at a rate sufficient to produce the nickel complex.

U.S. Patent No. 6,171,996 is disclosed, for example, in U.S. Patent Nos. 3,496,217; 3,631,191; 3,846,461; 3,847,959 and 3,903,120, which are incorporated herein by reference, discloses a zero valent nickel complex comprising a bidentate phosphite ligand prepared or produced according to techniques well known in the art. For example, a divalent nickel compound may be combined with a reducing agent to serve as a source of zero-nickel in the reaction. Suitable divalent nickel compounds are known to comprise compounds of the formula NiY ₂ - wherein Y is a halide, carboxylate, or acetylacetonate. Suitable reducing agents are known to include metal borohydrides, metal aluminum hydrides, metal alkyls, Zn, Fe, Al, Na, or H ₂ . As described in U.S. Patent No. 3,903,120, elemental nickel, preferably nickel powder, when combined with a halogenated catalyst, is also a suitable source of zero valent nickel.

Compared to single-phosphorus containing ligands, bidentate phosphorus ligands generally react more slowly with the nickel metal described in the references. One example of a suitable nickel metal is INCO Type 123 nickel metal powder (Chemical Abstract Service Registration Number 7440-02-0) derived from the decomposition of nickel carbonyl at elevated temperature.

Many nickel salts can be converted to nickel metal by reduction with hydrogen at elevated temperatures. Potential sources are nickel oxides, nickel formates, nickel oxalates, nickel hydroxides, nickel carbonates, and basic nickel carbonates (BNC). BNC production is described by RM Mallya, et al. the Journal of the Indian Institute of Science 1961, Vol. 43, Pages 44-157 and MA Rhamdhani et al., Metallurgical and Materials Transactions B 2008, Vol. 39B, pages 218-233 and 234-245.

Summary of the Invention

Bidentate ligands can be converted to nickel catalysts having particular advantages over nickel catalysts comprising monodentate ligands, particularly as olefin hydrocation catalysts. Unfortunately, INCO type 123 nickel metal powders have insufficient reactivity with some of these bidentate ligands. Therefore, there is a need for a nickel metal powder which is sufficiently reactive with a bidentate ligand and a method for producing the nickel metal powder.

Basic nickel carbonate (BNC) is a cheap and commercially available nickel source. However, the evaluation of BNC samples from different minerals and chemical vendors has revealed that the different BNC materials available lead to nickel metals with broad reactivity with phosphorus containing ligands to form nickel complexes.

The invention disclosed herein provides a basic nickel carbonate which is capable of producing nickel metal which is highly reactive with both monodentate and bidentate ligand containing ligands upon formation of the nickel metal complex. Also disclosed is a process for the preparation of basic nickel carbonates, since it has also been found that the precipitation conditions for the production of basic nickel carbonates can affect the activity of the nickel metal produced. The resulting nickel metal is useful for forming nickel metal complexes for preparing pentenenitrile and dinitrile by hydrocyanation.

In one aspect, (i) contacting the precipitant solution with a nickel solution to form a reaction mixture; And (ii) precipitating the nickel (II) composition from the reaction mixture; Wherein the nickel solution comprises nickel (II) ions and water, wherein the precipitant solution comprises (a) bicarbonate ions and water, (b) carbonate ions and water, and (c) ≪ / RTI > Wherein the molar ratio of bicarbonate ion to nickel ion in the reaction mixture is from about 0: 1 to about 2: 1 and the molar ratio of carbonate ion to nickel ion in the reaction mixture is from about 0: 1 to about 1.6: 1. ≪ / RTI >

In a further aspect, the precipitant solution is added to the nickel solution by, for example, gradual addition.

Another aspect of the present invention is a process for preparing a nickel complex of a phosphorus containing ligand by a process comprising reacting a nickel metal with a phosphorus containing ligand,

(i) contacting a nickel (II) salt dissolved in water with a precipitant selected from the group consisting of a bicarbonate salt, a carbonate salt, and combinations thereof with agitation to form a precipitate comprising the nickel (II) To form a reaction mixture; And

(ii) controlling the contact rate so that the water phase has a pH of from about 4.0 to about 7.5; and reducing the nickel (II) composition formed according to the process.

The carbon to nickel molar ratio of the thus formed nickel (II) composition may vary. In some embodiments, the carbon to nickel molar ratio of the nickel (II) composition is from about 0 to about 0.5.

The controlling step may further comprise controlling the amount of precipitant added to the nickel (II) salt (e.g., the type of nickel solution) dissolved in the water. The amount of precipitant added to the nickel (II) salt dissolved in water depends on the composition of the precipitant.

In some embodiments, the precipitant comprises a bicarbonate salt, e. G., A bicarbonate salt solution. The contact rate of the precipitant comprising a bicarbonate salt can be controlled such that the first molar ratio is from about 0.0 to about 2.0, wherein the first molar ratio is selected from the group consisting of bicarbonate in contact with the nickel (II) The total moles of salt is divided by the total moles of nickel (II) salt in the reaction mixture. For example, the first molar ratio may be from about 1.0 to about 1.9 at the end of contact with the precipitant of the nickel (II) salt dissolved in water.

In some embodiments, the precipitant comprises a carbonate salt, e. G., A carbonate salt solution. The contact rate of the precipitant comprising the carbonate salt can be controlled such that the second molar ratio is from about 0.0 to about 1.6, wherein the second molar ratio is the sum of the carbonate salt contacted with the nickel (II) salt dissolved in water Moles divided by the total moles of nickel (II) salt in the reaction mixture. For example, the second molar ratio may be about 0.8 to about 1.4 at the end of contact with the precipitant of the nickel (II) salt dissolved in water.

In some embodiments, the contacting is carried out in a precipitation reactor by feeding the precipitant solution to a precipitation reactor containing nickel (II) salts dissolved in water to form a reaction mixture. The feed of the precipitant solution to the precipitation reactor can be carried out, for example,

(a) the first molar ratio of the total moles of bicarbonate salt divided by the total moles of nickel (II) salt charged to the precipitation reactor is from about 0.0 to about 2.0; or

(b) the second molar ratio, which is the total molar amount of the carbonate salt contacted with the nickel (II) salt dissolved in water divided by the total moles of the nickel (II) salt charged in the precipitation reactor, is from about 0.0 to about 1.6 .

 During the process described herein for forming the nickel (II) composition, the temperature of the reaction mixture can be maintained, for example, from about 25 [deg.] C to about 90 [deg.] C. In addition, carbon dioxide can be added to the nickel (II) salt or reaction mixture dissolved in water.

In some embodiments, the methods disclosed herein may involve digesting a precipitate formed by mixing a nickel (II) salt dissolved in water with a precipitant. The aging can be performed by heating the reaction mixture containing the precipitate, for example, for a period of about 0.5 hours to about 24 hours, for example, from about 50 ° C to about 90 ° C.

In some embodiments, the precipitation of the nickel (II) composition from the reaction mixture, particularly when the precipitate comprises a bicarbonate salt, is selected from the group consisting of precipitation conditions (1), (2), and Can be carried out using two or more precipitation conditions: (1) reaction mixture temperature from about 60 DEG C to about 80 DEG C; (2) addition of carbon dioxide to the reaction mixture; And (3) a first molar ratio of from about 0.0 to about 1.6. In a further embodiment, each of conditions (1), (2), and (3) is used.

In some embodiments, the precipitation of the nickel (II) composition from the reaction mixture, especially when the precipitate comprises a carbonate salt, is carried out in the presence of two (2) selected from the group consisting of conditions (4), (5) (4) a reaction mixture temperature of from about 60 DEG C to about 80 DEG C; (5) addition of carbon dioxide to the reaction mixture; And (6) a second molar ratio of from about 0.0 to about 1.2. In a further embodiment, conditions (4), (5), and (6) are used.

After forming the precipitate, the process comprises separating the precipitated nickel (II) composition from the reaction mixture,

(a) washing the precipitated nickel (II) composition with water; And

(b) at least partially drying the precipitated nickel (II) composition.

For example, at least a portion of the washed precipitated nickel (II) composition from process step (a), at least a portion of the at least partially dried precipitated nickel (II) composition from process step (b) at least a portion of the washed and at least partially dried precipitated nickel (II) composition from (a) and (b) may be reduced to form a nickel metal.

In some embodiments, the phosphorus containing ligand for forming a complex with the nickel metal formed from the nickel (II) composition is selected from the group consisting of monodentate phosphite, monodentate phosphonite, monodentate phosphine, monodentate phosphine, bidentate phosphite, , Bidentate phosphinite, bidentate phosphine, mixed bidentate ligands, or any combination thereof; Wherein the mixed bidentate ligand is selected from the group consisting of phosphite-phosphonite, phosphite-phosphonite, phosphite-phosphine, phosphonate-phosphonite, phosphonate-phosphine, and phosphonite-phosphine Lt; / RTI > In some embodiments, the phosphorus containing ligand is a bidentate phosphite, a bidentate phosphonite, a bidentate phosphinite, a bidentate phosphine, a mixed bidentate ligand, or any combination of such members; When such a ligand is used to prepare a nickel complex, the reaction of the nickel metal with the phosphorus containing ligand further comprises a Lewis acid.

Another aspect of the invention is a process for preparing a nickel complex of a phosphorus containing ligand wherein the phosphorus containing ligand reacts with the nickel metal to form a metal complex of the phosphorus containing ligand; Characterized in that the nickel metal is produced by reducing the nickel (II) composition and the nickel (II) composition produces carbon dioxide upon heating. Nickel (II) compositions may be prepared, for example, by any of the methods described herein.

Justice

Digit: Each of the ligand molecules containing a single phosphorus atom that is capable of forming a nickel complex, which can include one or more ligands coupled to a single-digit nickel atom.

Bidentate : Each ligand molecule contains two phosphorus atoms, both of which can be bonded to a single nickel atom to form a nickel complex.

Phosphite : An organic phosphorus compound containing a trivalent phosphorus atom bonded to three oxygen atoms.

Phosphonite : an organic phosphorus compound comprising a trivalent phosphorus atom bonded to two oxygen atoms and one carbon atom.

Phosphinite : an organic phosphorus compound comprising a trivalent phosphorus atom bonded to one oxygen atom and two carbon atoms.

Phosphine : An organic phosphorus compound comprising a trivalent phosphorus atom bonded to three carbon atoms.

A novel nickel (II) composition comprising nickel, and a process for producing the same. In some embodiments, the nickel (II) composition comprises a basic nickel carbonate, also referred to as BNC. BNC, in particular the BNC prepared as described herein, is a suitable source of Ni (II) for the reduction and formation of ligand complexes in the preparation of a 0-nickel hydrocyanation catalyst, which is sometimes referred to herein as "BNC nickel ". By way of example, BNC has the formula _{[Ni (CO 3) x (} OH) y] z (H 2 O) _n can be described as the equation x = z - (y / 2 ); y = 2z - 2x; z = 1 to 100; And n = 0 to 400. The BNC may be referred to as comprising nickel (II) ions, carbonate ions, hydroxide ions, and water molecules. In some embodiments, the BNC nickel is synthesized using a source of Ni (II), such as Ni (II) salt. BNC nickel may be synthesized using the procedures disclosed herein. Certain types of BNC nickel, including BNC nickel produced by some of the procedures described in detail herein, can yield Ni (0) particularly suitable for the formation of nickel (0) complexes with phosphorus containing ligands. For example, the Ni (0) metal produced from the BNC prepared as described herein is particularly suitable for forming nickel complexes comprising the nickel disclosed herein and one or more phosphorus containing ligands. For example, Ni (0), which is particularly suitable for forming such nickel complexes, provides higher yields of nickel complexes. The nature of Ni (0), which is suitable for forming nickel complexes, can be selected, for example, to have a low carbon content, a large surface area, a small particle size, a small crystallite size (e.g., less than 89 nm) . Ni (0) can have a surface area of, for example, about 0.5 square meters per gram, 2 m 2 / g, 4, 6, 10, 20, 30, 40, about 50 m 2 / g, have. In some examples, Ni (0) with a surface area of about 2 m 2 / g, 5 m 2 / g, 10 m 2 / g, greater than 20 m 2 / g or greater than about 30 m 2 / g, forms a nickel complex with phosphorus containing ligand . For example, a low carbonate content, NiCO ₃ of less than about 1: having the properties, including weight ratio, or a any combination of C: Ni (OH) ₂ molar ratio, at least about 10: Ni of 1 BNC nickel can produce Ni (0) with low levels of carbon impurities, including carbon impurities due to carbonate impurities, thus producing Ni (0) suitable for nickel-ligand complex formation. Calcination of BNC nickel having a low carbonate content, a property comprising a molar ratio of NiCO ₃ : Ni (OH) ₂ of less than about 1, a mass ratio of Ni: C of at least about 10: 1, Or heating, carbon dioxide (CO ₂ ) is more readily produced and, therefore, is converted more completely into NiO, with less carbon impurities in the NiO, including carbonate impurities. By producing NiO with lower carbon content, including lower carbonate content, the improved NiO product is produced from BNC, where NiO has less carbon impurities.

Accordingly, there is disclosed herein a novel nickel-containing solid, including nickel metal, derived from a nickel (II) composition of basic nickel carbonate, and methods for making the same. The nickel (II) composition of BNC can be prepared by contacting the precipitant solution with a nickel solution (e.g., in a precipitation reactor) to form a reaction mixture; And (ii) precipitating a nickel (II) composition from the reaction mixture, wherein the nickel solution comprises nickel (II) ions and water, wherein the precipitant solution comprises (a) And water, (b) carbonate ion and water, and (c) mixtures thereof.

The amount of added precipitant and the proportion of precipitant added may vary. For example, the molar ratio of bicarbonate ion to nickel ion in the reaction mixture at the end of the feed may be from about 0.5: 1 to about 1.6: 1, from about 0.5: 1 to about 1.2: 1, from about 1.0: From about 1: 1 to about 1.6: 1, from about 1: 1 to about 1: 1, from about 1: 1 to about 1: 1, from about 1.2: 1 to about 1.9: 1, from about 0.8: 1 to 2: 1, including from about 0.8: 1 to about 1.4: 1, from about 0.8: 1 to about 1.4: 1, and from about 0.8: 1 to about 1.2: 1. The molar ratio of carbonate ion to nickel ion in the reaction mixture at the end of the feed is from about 0.5: 1 to about 1.4: 1, from about 1: 1 to about 1.2: 1, from about 0.8: 1 to about 1.4: 1: 1 to about 1.4: 1, and from about 0.8: 1 to about 1.2: 1 in a ratio of from about 1: 1 to about 1.6: 1, from about 1.0: 1 to about 1.6: 1, from about 1.0: , And may range from 0.3: 1 to 1.6: 1. Blends of bicarbonate and carbonate may also be used in the precipitant solution. As will be described in more detail below, the molar ratio has a surprising effect on the effectiveness of the resulting nickel metal reacting with the phosphorus ligand.

The ratio of precipitant addition may vary. The precipitant may be continuously added to or supplied to a nickel solution (e.g., a nickel salt in water). In some embodiments, the precipitant may be added or supplied intermittently to the nickel solution. To avoid the introduction of an excess of precipitant (e. G., Excess bicarbonate or carbonate), the precipitant may be added gradually or intermittently in small amounts.

The precipitation reactor may be any suitable sealed vessel, such as a tank or pipe. The precipitation can be carried out in batch or continuous mode. In addition, the reaction mixture may be stirred before and / or during precipitation of the nickel (II) composition. For example, agitation may be performed by mechanical stirring, pump circulation loop, flow-through static mixing, or ultrasonic. The use of high shear during precipitation can prevent particle agglomeration and provide smaller generated BNC nickel particles. Thus, in some embodiments, the precipitant is added to the nickel solution with high shear agitation. Reactor design, stirring design, and application of high power to stirring are examples of factors that can cause high shear agitation of the reaction mixture during precipitation.

The nickel (II) composition may be used in an amount of from about 20 캜 to about 90 캜, from about 20 캜 to about 70 캜, from about 20 캜 to about 50 캜, from about 50 캜 to about 90 캜, RTI ID = 0.0 > 0 C < / RTI > to about 90 C, including about < RTI ID = 0.0 > 75 C. < / RTI > In some embodiments, increased temperature during precipitation can reduce the fraction of carbonate ions in the resulting BNC nickel. Moreover, the nickel (II) composition can be precipitated from the reaction mixture in the presence of added carbon dioxide. For example, carbon dioxide may be added to the precipitation reactor, added to the nickel solution, added to the precipitant solution, added to the reaction mixture, or any combination thereof. In addition, the precipitant solution may be supplied over a period of about 30 minutes to about 60 minutes, and may be carried out in a semi-continuous or continuous mode. In addition, the precipitant solution may be added to the nickel solution of the precipitation reactor in semi-continuous or continuous mode, for example, gradual addition. In some embodiments, the fraction of carbonate ions in the BNC nickel precipitate produced due to the use of higher pH during precipitation can be reduced. For example, a pH value of about 4, 5, 6, 7, 8, or about 9, or greater, can be used. As an example, the pH increases from about 4.9 to about 5.8 during precipitation.

The reaction mixture may also be aged by heating the reaction mixture at about 50 ° C to about 90 ° C for a period of about 0.25 hours to about 24 hours after contacting the precipitant solution with the nickel solution. Other suitable temperature ranges include about 60 캜 to about 80 캜 and about 65 캜 to about 75 캜. Under the conditions, the longer the aging time, the larger the BNC nickel particles in the resulting precipitate. Other suitable times may range from about 0.5 hours to about 20 hours, including from about 0.5 hours to about 14 hours, from about 1 hour to about 12 hours, and from about 1 hour to about 8 hours. In some embodiments, the reaction mixture is heated to about 50 ° C to about 90 ° C for a period of about 0.25 hours to about 2 or 3 or 4 hours.

The disclosed nickel (II) composition method comprises, after the precipitation step, washing the precipitated nickel (II) composition with water; And at least partially drying the precipitated nickel (II) composition. For example, the nickel (II) composition precipitated from the reaction mixture is separated from the reaction mixture by filtration or decantation, and the resulting precipitated nickel (II) composition is washed with water by filtration or decantation, The resulting precipitated nickel (II) composition is dried by water evaporation at about 60 캜 to about 100 캜. Drying may be carried out under ambient pressure or under vacuum, and in the presence of an inert gas, such as nitrogen. In some embodiments, increasing the drying time can increase the fraction of carbonate ions in the nickel oxide produced from the resulting BNC nickel, or BNC nickel.

Nickel solutions containing nickel (II) ions and water can be prepared by dissolving nickel (II) salts in water. Nickel salts of any salt soluble in water, may be, for example, NiCl _2, NiSO _4, and Ni (NO _{3) 2.}

In some embodiments, precipitants can be used to produce BNC (nickel containing) precipitates. The precipitant comprises bicarbonate and / or carbonate ions with counter ions of sodium, potassium, or ammonium. A precipitant solution containing a bicarbonate ion can be prepared by dissolving a bicarbonate salt, such as NaHCO ₃ and NH ₄ HCO ₃ , in water. Alternatively, or additionally, the precipitant may be prepared in situ by dissolving CO ₂ and alkali metal hydroxide or ammonia in water in a known manner. Likewise, precipitant solutions containing carbonate ions can be prepared by dissolving carbonate salts, such as Na ₂ CO ₃ , or by dissolving CO ₂ and alkali metal hydroxides in water in a known manner, . ≪ / RTI > The anion of the nickel salt and the cation of the bicarbonate or carbonate salt are selected such that the salt (e.g., NaCl) resulting from the precipitation, including both cations and anions from the reaction mixture, is soluble in water of the reaction mixture . This selection provides a method for separating the salt product from a precipitated nickel (II) composition.

Also disclosed are methods for making nickel-containing solids comprising nickel metal. The method comprises: (i) providing a nickel (II) composition as described above; And (ii) reducing at least a portion of the nickel (II) composition of step (i) using a reducing agent to form a nickel containing solid comprising nickel metal, wherein the nickel containing solid comprises a bidentate ligand Thereby effectively reacting to form a nickel complex of the phosphorus-containing ligand. Nickel-containing solids are more reactive than phosphorus-containing ligands than nickel-containing solids prepared by other methods, such as INCO type 123 nickel metal powders, nickel oxides, nickel formates, nickel oxalates, nickel hydroxides, nickel carbonates Big. High reactivity is due in part to the BNC process as well as the reduction process described above. The reducing agent may be hydrogen, carbon dioxide, carbon monoxide, methane, ammonia, hydrogen sulphide (only some non-limiting examples of suitable reducing agents are listed).

As noted above, the amount of bicarbonate or carbonate ion supplied for the charged nickel (II) ion has a significant effect on the reactivity of the phosphorus containing ligand with the resultant nickel-containing solids for preparing nickel complexes . Due to the high cost of nickel, manufacturers of BNC type nickel (II) compositions will add excess precipitant solution to recover as much nickel as economically feasible. Surprisingly, however, it has been found that the use of excess precipitant produces a less reactive nickel metal in the case of the phosphorus-ligand complex reaction. Thus, in some embodiments, no excess of precipitant is added to the amount of nickel. When a reduced level of precipitant is used, highly reactive nickel is produced, presumably more nickel (II) ions remain dissolved in the water of the resulting reaction mixture.

It has also been found that precipitated nickel (II) compositions prepared using bicarbonate ions are filtered and washed much faster than precipitated nickel (II) compositions made using carbonate ions. In addition, the filtered precipitated nickel (II) composition prepared using the bicarbonate ion is dried to a soft powder with little shrinkage. For this reason, the preparation of nickel-containing solids using non-carbonate ions provides more desirable properties for the downstream treatment and handling of dried precipitated nickel (II) compositions.

Reducing the nickel (II) composition with a reducing agent to form a nickel metal-containing solid is carried out at a temperature in the range of from about 150 캜 to about 700 캜, including from about 300 캜 to about 500 캜, and from about 350 캜 to about 450 캜 . In another aspect, the reduction temperature is from about 350 캜 to about 1500 캜, including from about 350 캜 to about 450 캜. The reducing pressure may range from about 0.01 atmospheres to about 100 atmospheres. The reduction may be carried out for a period of at least about 30 minutes using a stoichiometric excess of a reducing agent such as hydrogen, although one mole of hydrogen per mole of nickel (II) composition to be reduced is the theoretical and stoichiometric amount required for complete reduction. For example, the reduction period may be from about 1 to about 2 hours, using the mole of nickel atoms in the nickel oxide of the molar ratio 2: 1 hydrogen to nickel composition.

The disclosed nickel containing solids can react with phosphorus containing ligands to form nickel complexes of phosphorus containing ligands. Such complexes are useful as catalyst precursors in at least one of the following reactions: (1) reacting 1,3-butadiene with hydrogen cyanide to produce 2-methyl-3-butenitrile and 3-pentenenitrile; (2) reacting 2-methyl-3-butenitrile to produce 3-pentenenitrile; (3) reacting 3-pentenenitrile with hydrogen cyanide in the presence of a Lewis acid to produce adiponitrile; And (4) reacting the 2-pentenenitrile with hydrogen cyanide in the presence of a Lewis acid to produce 3-pentenenitrile, 4-pentenenitrile, and adiponitrile.

Phosphorus containing ligands may be monodentate phosphites, monodentate phosphonites, monocline phosphinites, monoclinic phosphines, bidentate phosphites, bidentate phosphonites, bidentate phosphinites, or bidentate phosphines, and any combination of these members have. In addition, the phosphorus containing ligand can be monodentate phosphite to form a monodisperse nickel complex, and then the monodisperse nickel complex can be combined with the bidentate phosphorus ligand. Likewise, the phosphorus containing ligand may be a bidentate phosphite further comprising monodentate phosphite.

When the phosphorus containing ligand is a bidentate phosphite, the bidentate phosphite may be selected from the group consisting of the group consisting of formula (Ia), (Ib), (Ic), or any combination of these members:

<Formula Ia>

(Ib)

<Formula I>

In formulas Ia, Ib and Ic,

R ¹ is phenyl which is unsubstituted or substituted by one or more C ₁ to C ₁₂ alkyl, C ₁ to C ₁₂ alkoxy groups, or groups of formulas A and B, or - (CH ₂ ) _n OY ² ; Or naphthyl unsubstituted or substituted with one or more C ₁ to C ₁₂ alkyl or C ₁ to C ₁₂ alkoxy groups, or groups of formulas A and B, or - (CH ₂ ) _n OY ² ; Or 5,6,7,8-tetrahydro-1-naphthyl;

&Lt; Formula (A)

&Lt; Formula B >

In Formulas A and B,

Y ¹ is independently H, C ₁ to C ₁₈ Is selected from the group of alkyl, cycloalkyl, or aryl, Y ² is independently selected from the group of C ₁ to C ₁₈ alkyl, cycloalkyl, or aryl, Y ³ is independently selected from the group of O or CH ₂ ; , n = 1 to 4;

In formulas Ia, Ib and Ic,

OZO and OZ ¹ -O are independently selected from the group consisting of formulas II, III, IV, V, and VI:

&Lt;

<Formula III>

In formulas (II) and (III)

R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are independently selected from the group consisting of H, C ₁ to C ₁₂ alkyl, and C ₁ to C ₁₂ alkoxy; X is O, S, or CH (R ¹⁰ );

R ¹⁰ is H or C ₁ to C ₁₂ Alkyl;

(IV)

(V)

In formulas IV and V,

R ²⁰ and R ³⁰ are independently selected from the group consisting of H, C ₁ to C ₁₂ alkyl, and C ₁ to C ₁₂ alkoxy, and CO ₂ R ¹³ ;

R ¹³ is unsubstituted or C ₁ to C ₄ C ₁ to C ₁₂ alkyl or C ₆ to C ₁₀ aryl, substituted by alkyl;

W is O, S, or CH (R &lt; ¹⁴ &gt;);

R ¹⁴ is H or C ₁ to C ₁₂ Alkyl;

&Lt; Formula (VI)

In Formula VI,

R ¹⁵ is selected from the group consisting of H, C ₁ to C ₁₂ alkyl, and C ₁ to C ₁₂ alkoxy and CO ₂ R ¹⁶ ; R ¹⁶ is C ₁ to C ₁₂ alkyl or C ₆ to C ₁₀ aryl which is unsubstituted or substituted by C ₁ to C ₄ alkyl.

When the phosphorus containing ligand is a bidentate phosphite, the bidentate phosphite may be selected from the group consisting of Formulas VII and VIII:

(VII)

&Lt; Formula (VIII)

Where

R ⁴¹ and R ⁴⁵ are independently selected from the group consisting of C ₁ to C ₅ hydrocarbyl, and R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are each independently H and C ₁ to C ₄ Selected from the group consisting of hydrocarbyl; or

The phosphorus containing ligand

R ⁴¹ is methyl, ethyl, isopropyl or cyclopentyl;

R ⁴² is H or methyl;

R ⁴³ is H or C ₁ to C ₄ hydrocarbyl;

R ⁴⁴ is H or methyl;

R ⁴⁵ is methyl, ethyl or isopropyl;

R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are independently a bidentate phosphite selected from the group consisting of: H and C ₁ to C ₄ hydrocarbyl;

The phosphorus containing ligand

R ⁴¹ , R ⁴⁴ , and R ⁴⁵ are methyl;

R ⁴² , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are H;

R ⁴³ is C ₁ to C ₄ hydrocarbyl; or

R ⁴¹ is isopropyl;

R ⁴² is H;

R ⁴³ is C ₁ to C ₄ hydrocarbyl;

R ⁴⁴ is H or methyl;

R ⁴⁵ is methyl or ethyl;

R ⁴⁶ and R ⁴⁸ are H or methyl;

R ⁴⁷ is a bidentate phosphite selected from the group consisting of H, methyl or tertiary butyl;

The phosphorus containing ligand

R ⁴¹ is isopropyl or cyclopentyl;

R ⁴⁵ is methyl or isopropyl;

R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are H; or a bidentate phosphite selected from the group consisting of formula VII and VIII;

The phosphorus containing ligand is R ⁴¹ is isopropyl; R ⁴² , R ⁴⁶ , and R ⁴⁸ are H; R ⁴³ , R ⁴⁴ , R ⁴⁵ , and R ⁴⁷ are methyl.

Furthermore, when the phosphorus containing ligand is a bidentate phosphite, the bidentate phosphite may have the formula IX

<Formula IX>

(Wherein R ¹⁷ is isopropyl, R ¹⁸ is hydrogen, and R ¹⁹ is methyl); And X

(X)

(Wherein R ¹⁷ is methyl, R ¹⁸ is methyl, and R ¹⁹ is hydrogen).

Additional bidentate ligands, ligand complexes, and methods for their preparation are disclosed in U.S. Patent No. 6,171,996, which is incorporated herein by reference in its entirety.

In any of the foregoing processes, including reacting a nickel-containing solid with a monoclinic phosphorus containing ligand, reacting the nickel-containing solids with the mono phosphorus containing ligand comprises reacting PX ₃ , R ¹⁷ PX ₂ , R ¹⁸ OPX ₂ , [R ^{19 ] [R 20] PX, [} R 21] [R 22 O] PX, and ^{[R 23 O] [R 24} O] PX - wherein ^{R 17, R 18, R 19} , R 20, R 21, R 22, R ²³ , and R ²⁴ are independently selected from the group consisting of C ₁ to C ₁₈ hydrocarbyl radicals, and each X is a halide selected from the group consisting of chloride, bromide, and iodide. Lt; RTI ID = 0.0 &gt; halogenation &lt; / RTI &gt;

The bidentate phosphorus ligand may further comprise at least one Lewis acid promoter. The Lewis acids are selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium, lanthanum, europium, ytterbium, tantalum, And an inorganic or organic metal compound containing an element selected from the group consisting of: For example, the at least one Lewis acid is selected from the group consisting of zinc chloride, ferrous chloride, or a combination of zinc chloride and ferrous chloride.

The reaction between the nickel-containing solid and the phosphorus containing ligand may further comprise an organic nitrile, such as a pentenenitrile. For example, the organonitrile may be selected from the group consisting of 2-pentenenitrile, 3-pentenenitrile, 4-pentenenitrile, 2-methyl-3-butenenitrile, , And ethyl succinonitril. &Lt; / RTI &gt;

The preparation of nickel complexes or nickel complexes from the reaction of monodentate and bidentate ligands with the nickel-containing solids of the present invention can be carried out as described in U.S. Provisional Application No. 61 / 287,757 and the following examples. For example, a 5 wt% solution of a bidentate phosphorus ligand in pentene nitrile solvent (0.5-2.5 mol of Lewis acid per mole of bidentate ligand), further comprising a Lewis acid such as ZnCl ₂ , (For example, 4.0 wt% of a nickel-containing solid). Temperatures between 60 [deg.] C and 80 [deg.] C provide acceptable reaction rates. Sufficient stirring may be used to suspend nickel-containing solids in such reaction mixture.

Example

Definition of abbreviations:

ADN = adiponitrile; Aryl = an unsubstituted or substituted aryl radical containing from 6 to 18 carbon atoms; BD = 1,3-butadiene; hrs = time; BNC = basic nickel carbonate; 2 M 3 BN = 2-methyl-3- butenenitrile ; MGN = 2-methylglutaronitrile; Pentene nitrile or the nitrile-pentene = (if it is not specifically limited to) 4PN, 3PN, 2PN, 2M3BN , and 2M2BN isomers; 2- pentenenitrile (if not specifically limited) comprising both 2 PN = c2PN and t2PN isomers; 3 pentene nitrile, including but not limited to 3 PN = c3PN and t3PN; 4 PN = 4-pentenenitrile; ppm = parts per million by weight; wt % = weight%.

Various aspects of the disclosed BNC compositions, nickel containing solids, phosphorus containing nickel metal complexes, and methods of making them can be further understood in light of the following non-limiting examples. In the following paragraphs, all references are incorporated herein by reference.

Two digits  Phosphorus containing Ligand

Examples 1 to 13 used ligand A, which is a bidentate phosphite ligand. The ligand A can be prepared by any suitable synthetic means known in the art. For example, 3,3'-diisopropyl-5,5 ', 6,6'-tetramethyl-2,2'-biphenol may be prepared by the procedure disclosed in U.S. Published Patent Application 2003/0100802 Wherein the 4-methylthymol is oxidatively coupled with a substituted chlorophenol-TMEDA complex (TMEDA is N, N, N ', N'-tetramethylethylenediamine) and a substituted biphenol in the presence of air (oxidative coupling). The phosphorochloridite [(CH ₃ ) ₂ C ₆ H ₃ O] ₂ PCl of 2,4-xylenol can be prepared, for example, by the procedures described in US Published Patent Application No. 2004/0106815 . In order to selectively form these phosphorochloridites, anhydrous triethylamine and 2,4-xylenol can be added separately and simultaneously in controlled manner to PCl ₃ dissolved in an appropriate solvent under temperature-controlled conditions . The reaction of such phosphorochloridite with 3,3'-diisopropyl-5,5 ', 6,6'-tetramethyl-2,2'-biphenol to form the desired ligand A is described, for example, For example, in accordance with the method disclosed in U.S. Patent No. 6,069,267, which is incorporated herein by reference. Phosphorochloridite can react with 3,3'-diisopropyl-5,5'6,6'-tetramethyl-2,2'-biphenol in the presence of an organic base to form ligand A, May be isolated according to techniques well known in the art, e.g. as described in U.S. Patent No. 6,069,267, for example. Ligand A is an example of a compound of Formula I, and the ligand A solution in the following 3PN solvent does not contain any halogenation catalyst of U.S. Patent No. 3,903,120.

Ligand  A

Example 16 used a mixture of different monodentate phosphites, and ligand B, which is derived from the reaction of m-cresol / p-cresol / phenol mixture with PCl ₃ . Ligand B is an example of a compound of formula II.

Ligand  B

(Where x + y + z = 3).

Example  One

One liter of a NiCl ₂ solution (250 mL, 0.25 mol of NiCl ₂ ) in water was charged into a 1-liter beaker, and the solution was magnetically stirred while being heated to 70 ° C. While maintaining the temperature, the reaction mixture was sparged with the added CO ₂ gas at a rate of 100 mL / min, so that a precipitant solution containing bicarbonate ions (25.2 gm of NaHCO ₃ dissolved in 400 mL of water, 0.30 Mol NaHCO ₃ ) was continuously fed to the beaker at a rate of 10 mL / min. At the end of the addition of the precipitant solution, the total molar amount of the supplied carbonate ion per mol of the charged nickel ion was 1.2: 1. Due to this addition, a solid product, nickel-containing BNC composition, precipitated from the reaction mixture. Then, after all the precipitant solution was added, the flow of the carbon dioxide gas to the reaction mixture was terminated, and the resulting reaction mixture slurry was aged at 70 DEG C for 2 hours. Then, at the end of this aging period, the slurry was filtered using a sintered glass filter, and the solid filter cake was washed with 200 mL of water. The solid filter cake was then dried overnight in a vacuum oven at 80 DEG C with nitrogen sweeping through a vacuum oven.

Next, 15 grams of the dried solid filter cake was placed inside a reaction tube that could be heated in an electric furnace installed in a laboratory fume hood. The hydrogen gas flow to the reaction tube was then set to 0.2 liters / minute (about 1 atmosphere) and any hydrogen exhaust gas from the reaction tube flowed through the bubble generator. The temperature of the tube furnace was then increased to a final temperature of 400 占 폚 at a rate of 10 占 폚 / min and then maintained at 400 占 폚 for 1 hour, after which the reaction tube was cooled under a hydrogen flow. After lowering the reaction tube temperature to below 50 &lt; 0 &gt; C, the flow to the reaction tube was converted to nitrogen gas and hydrogen was purged from the reaction tube. The valve on the reaction tube was then closed to prevent exposure of the resulting nickel-containing solids, including nickel metal, to air, and the entire reaction tube was transferred to a nitrogen-filled drying box and the nickel-containing solids were poured into the bottle. These nickel containing solids were observed to be attracted to magnets and thus contained nickel metal. Exposure of such nickel containing solids to air reduced the rate of the following reactions and / or allowed the nickel containing solids to burn in air to form nickel oxides.

Further, these nickel-containing solid 3.2 gm, 5% by weight of 3PN ligand A solution of 80 gm, and anhydrous ZnCl ₂ 0.50 gm, was placed in a bottle reactor containing a magnetic stir bar, a nickel complex in such a nitrogen dry box filled . Nickel-containing solids were not soluble in this reaction mixture. The reaction mixture was then rapidly heated to 80 ° C with magnetic stirring and the filtered sample was drained from the reaction mixture after 30 minutes to give 1460 as a nickel complex of ligand A dissolved in 3PN according to UV visible or LC analysis ppm &lt; / RTI &gt; of nickel. For example, a calibrated absorption method was used to detect the soluble divalent nickel complex (ligand A) Ni (η ³ -C ₄ H ₇ ) C≡N-ZnCl ₂ by absorption at a wavelength of 380 nanometers. This absorption method was calibrated for LC analysis for total soluble nickel.

Example  2 to 5

The amount of NaHCO ₃ dissolved in 400 mL of water was controlled so that the molar ratio of the bicarbonate ion supplied per mol of nickel ion charged was changed from 1.6: 1 to 2.0: 1 to prepare a precipitant solution. The general procedure of Example 1 was repeated in Examples 2-5. The results from the reaction of the resulting nickel-containing solid with the ligand A solution and ZnCl ₂ are given in Table 1.

Examples 1 to 5 illustrate that the reactivity of the resulting nickel-containing solids with phosphorus containing ligands to form soluble nickel complexes decreases as the amount of supplied bicarbonate ions increases relative to the charged nickel ions. It is. That is, a greater amount of nickel complex was formed when this first molar ratio (supplied bicarbonate ion mole / charged nickel ion mole) was 0.0: 1 to 2.0: 1.

Example  6

Example 2 was repeated except that there was no sparging of CO ₂ gas through the reaction mixture during the feeding of the sodium hydrogencarbonate solution to the 1 liter beaker containing the nickel ion. As shown in Table 2, when a solid product precipitated in the presence of added CO ₂ gas, a greater amount of nickel complex was formed from the reaction of the resulting nickel-containing solid with the ligand A solution and ZnCl ₂ .

Example  7 and 8

Example 2 was repeated except that the heated NiCl ₂ solution, the reaction mixture during the continuous feeding of the precipitant solution to the 1 liter beaker, and the temperature of the aging period were 50 ° C for Example 7 and 90 ° C for Example 8 Respectively. Compared with Example 2 (see Table 3), when the solid product precipitates at 70 ° C rather than 50 ° C or 90 ° C, a greater amount of nickel complex from the reaction of the ligand A solution and ZnCl _{2 with} the resulting nickel- .

Example  9

Example 2 was repeated except that NiCl ₂ was replaced by NiSO ₄ . That is, the precipitant solution of Example 2 was continuously supplied to 1 mole of NiSO ₄ solution (250 mL, 0.25 mol NiSO ₄ ) in water at 70 ° C. Similar to the solid product precipitated from NiCl ₂ , when the solid product precipitated from the NiSO ₄ solution, an equivalent amount of nickel complex formed after 30 minutes from the reaction of the resultant nickel-containing solid with the ligand A solution and ZnCl ₂ (nickel 1465 ppm).

Example  10

One liter of a NiSO ₄ solution (250 mL, 0.25 mol NiSO ₄ ) in water was charged into a 1-liter beaker, and the solution was magnetically stirred while being heated to 70 ° C. While maintaining this temperature, a precipitant solution containing carbonate ions (21.2 gm of Na ₂ CO ₃ dissolved in 400 mL of water, 0.20 molar Na ₂ CO ₃ ) was continuously fed to the beaker at a rate of 10 mL / min , The reaction mixture was not sparged with CO ₂ gas. At the end of the addition of the precipitant solution, the total molarity of the carbonate ion supplied per mol of the charged nickel ion was 0.8. This addition also caused the solid product to precipitate from the reaction mixture. After all precipitant solutions were then added, the resulting reaction mixture slurry was aged at 70 ° C for 2 hours. Then, at the end of this aging period, the slurry was filtered using a sintered glass filter, and the solid filter cake was washed with 200 mL of water. The solid filter cake was then dried in a vacuum oven at 80 DEG C overnight while sweeping nitrogen through a vacuum oven.

The hydrogen flow at elevated temperature as described in Example 1 reduced 15 grams of the dried solid filter cake. Nickel complexes were also prepared as described in Example &lt; RTI ID = 0.0 &gt; 1. &lt; / RTI &gt; The filtered sample was found to be released from the reaction mixture in the bottle reactor after 30 minutes and contained 1420 ppm nickel as the nickel complex of ligand A dissolved in 3PN according to UV visible or LC analysis.

Example  11 to 13

The general procedure of Example 10 was repeated in Examples 11-13. In other respects, the precipitant solution was prepared by controlling the amount of Na ₂ CO ₃ dissolved in 400 mL of water to change the total molar ratio of carbonate ions supplied per mol of charged nickel ion from 1.0: 1 to 1.6: 1 . The results from the reaction of the resultant nickel-containing solid with the ligand A solution and ZnCl ₂ are given in Table 4.

Examples 10-13 show that the reactivity of the resulting nickel-containing solids with the phosphorus containing ligand to form soluble nickel complexes may decrease as the amount of carbonate ion supplied increases for the charged nickel ions . That is, when this second molar ratio (molar carbonate ion supplied / molar nickel ion charged) was between 0.0 and 1.6, a larger amount of nickel complex was formed.

Example  14

Example 5 was repeated except that the order of addition to the solid precipitation reaction in a 1 liter beaker was reversed. That is, 1 mol of NiCl ₂ solution was added to the precipitant solution to precipitate the solid product. After the reaction with the resulting nickel-containing solid and the ligand A solution of 3PN and ZnCl ₂ at 400 ° C, the resulting nickel-containing solid was reacted with the filtrate discharged from the reaction mixture, The sample was found to contain 0 ppm of nickel as the nickel complex of ligand A dissolved in 3PN.

Example  15

At constant settling temperatures, the weight of the dried solid filter cake was also increased by the addition of the supplied bicarbonate (Examples 1-9, Table 5) or carbonate ions (Examples 10-13, 6).

In addition, as described in Examples 1 to 14, when the solid product was precipitated using carbonate ions compared to the use of a bicarbonate ion, the precipitated solid product was filtered and the solid filter cake was subjected to displacement washing Which is generally observed to take more time. For example, under equivalent filtration conditions, for the solid product of Example 11 precipitated with carbonate ions, the filtration time was 14 minutes and the displacement wash time was 40 minutes. However, for solid products precipitated with bicarbonate ions, both the filtration time and the displacement wash time could each be less than one minute.

Example  16

Examples 1 to 13 to the nickel-containing solid phosphite ligand B and one place of 3PN reaction solvent, in the absence of a Lewis acid such as ZnCl _2, thereby forming a nickel complex in which 0 contains a nickel and a ligand B.

Example  17

After ZnCl ₂ was at least partially separated from the nickel complexes of Examples 1 to 12, the nickel complex of ligand A was contacted with BD and HC≡N in the reaction zone. 3PN, 2M3BN, or a combination thereof. The same nickel complex also reacted with 2M3BN to produce 3PN.

The nickel complex of ligand B of Example 16 was contacted with HC? N and BD in the reaction zone. 3PN, 2M3BN, or a combination thereof. The same nickel complex also reacted with 2M3BN to produce 3PN.

In the presence of a Lewis acid promoter such as ZnCl ₂ , the soluble nickel complexes of ligand A from the disease reactors of Examples 1-12 were contacted with HC≡N and 3PN in the reaction zone. The catalyst formed a conversion of more than 90% of 3PN to dinitriles including ADN, MGN, and ESN (95-96% ADN dispersion). The ADN dispersion is equivalent to 100% * ADN weight% / (ADN weight% + MGN weight% + ESN weight%), as determined by gas chromatography (GC).

In the presence of a Lewis acid promoter such as ZnCl ₂ , the soluble nickel complexes of ligand A from the disease reactors of Examples 1-12 were contacted with HC≡N and 2PN in the reaction zone. The catalyst formed a conversion of some of the 2PN to 3PN, 4PN, and ADN.

ZnCl _2, the formula as disclosed in triphenylboron, or U.S. Patent No. 4,749,801 _{[Ni (C 4 H 7 C≡N} ) 6] [(C 6 H 5) 3 BC≡NB (C 6 H 5) 3] _In the presence of a Lewis acid promoter such as the compound of ₂ , the nickel complex of Example 16 was contacted with HC? N and 3PN in the reaction zone. The catalyst formed a conversion of 3PN to dinitriles, including ADN, MGN, and ESN, where ADN is the major dinitrile product.

The present invention has been described above with respect to various aspects of the disclosed nickel (II) compositions, basic nickel carbonates, and methods for their preparation. Obvious modifications and changes will occur to the reader upon reading and understanding the preceding detailed description. It is intended that the invention be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims.

Claims (20)

A method for preparing a nickel complex of a phosphorus containing ligand, including reacting a nickel metal with a phosphorus containing ligand, wherein the nickel metal is
(i) contacting the nickel (II) salt dissolved in water with a precipitant selected from the group consisting of bicarbonate salts, carbonate salts, and combinations thereof while stirring to form precipitates and water phases comprising the nickel (II) composition. Forming a reaction mixture comprising; And
and (ii) reducing the nickel (II) composition formed according to a process comprising controlling the contact rate to bring the aqueous phase to a pH of about 4.0 to about 7.5. The method of claim 1, wherein the controlling step further comprises controlling the amount of precipitant added to the nickel (II) salt dissolved in water. The process of claim 1, wherein the precipitant comprises a bicarbonate salt, the contacting rate is controlled such that the first molar ratio is from about 0.5 to about 2.0, and the first molar ratio controls the total moles of the contacted bicarbonate salt in the reaction mixture. Dividing by the total moles of heavy nickel (II) salt. The method of claim 1 wherein the precipitant comprises a carbonate salt, the contacting rate is controlled such that the second molar ratio is from about 0.5 to about 1.6, and the second molar ratio is in contact with the carbon (II) salt dissolved in water. The total moles of carbonate salt divided by the total moles of nickel (II) salt in the reaction mixture. The process of claim 1 wherein the contacting is carried out in a precipitation reactor by feeding the precipitant solution to a precipitation reactor containing nickel (II) salt dissolved in water to form a reaction mixture,
Supply of precipitant solution
(a). A first molar ratio of about 0.5 to about 2.0, wherein the total moles of bicarbonate salt divided by the total moles of nickel (II) salt charged to the precipitation reactor; or
(b). And a second molar ratio of about 0.5 to about 1.6, wherein the total moles of carbonate salt contacted with the nickel (II) salt dissolved in water divided by the total moles of nickel (II) salt charged to the precipitation reactor. The method of claim 1, further comprising maintaining the reaction mixture temperature at about 25 ° C. to about 90 ° C. 7. The method of claim 1, further comprising adding carbon dioxide to the nickel (II) salt or reaction mixture dissolved in water. The method of claim 1, further comprising aging the precipitate by heating the reaction mixture to about 50 ° C. to about 90 ° C. for a period of about 0.5 hour to about 24 hours. The process of claim 3 further comprising precipitating the nickel (II) composition from the reaction mixture using at least two precipitation conditions selected from the group consisting of precipitation conditions (1), (2), and (3). :
(1) a reaction mixture temperature of about 60 ° C. to about 80 ° C .;
(2) addition of carbon dioxide to the reaction mixture; And
(3) a first molar ratio of about 0.5 to about 1.6. The process of claim 4 further comprising precipitating the nickel (II) composition from the reaction mixture using at least two precipitation conditions selected from the group consisting of precipitation conditions (4), (5), and (6). :
(4) a reaction mixture temperature of about 60 ° C. to about 80 ° C .;
(5) addition of carbon dioxide to the reaction mixture; And
(6) a second molar ratio of about 0.5 to about 1.2. 10. The method of claim 9, using conditions (1), (2), and (3). The method according to claim 10, using conditions (4), (5), and (6). The method of claim 3, wherein the first molar ratio is about 1.0 to about 1.9 at the end of the contact. The method of claim 4, wherein the second molar ratio is about 0.8 to about 1.4 at the end of the contact. The process of claim 1, wherein the precipitated nickel (II) composition is separated from the reaction mixture, followed by
(a) washing the precipitated nickel (II) composition with water; And
(b) further comprising at least one process step selected from the group consisting of at least partially drying the precipitated nickel (II) composition. The process of claim 15, wherein at least a portion of the washed precipitated nickel (II) composition from process step (a), at least a portion of the at least partially dried precipitated nickel (II) composition from process step (b), or At least a portion of the washed and at least partially dried precipitated nickel (II) composition from process steps (a) and (b) is reduced to form nickel metal. The process of claim 1 wherein the carbon to nickel molar ratio of the nickel (II) composition is from about 0 to about 0.5. 2. The method of claim 1, wherein the phosphorus containing ligand is monodentate phosphite, monodentate phosphonite, monodentate phosphinite, monodentate phosphine, monodentate phosphite, monodentate phosphonite, monodentate phosphinite, monodentate phosphine, mixed monodentate ligand , Or any combination thereof;
Mixed bidentate ligands are the group consisting of phosphite-phosphonite, phosphite-phosphinite, phosphite-phosphine, phosphonite-phosphinite, phosphonite-phosphine, and phosphinite-phosphine Selected from. The method of claim 18, wherein the phosphorus containing ligand is bidentate phosphite, bidentate phosphonite, bidentate phosphinite, bidentate phosphine, mixed bidentate ligand, or any combination of these members; Reacting the nickel metal with a phosphorus containing ligand further comprises the addition of a Lewis acid. A method of making a nickel complex of a phosphorus containing ligand, wherein the phosphorus containing ligand reacts with the nickel metal to form a nickel complex of the phosphorus containing ligand; Wherein the nickel metal is produced by reducing the nickel (II) composition, wherein the nickel (II) composition produces carbon dioxide upon heating.