CN115124575B - Preparation method of PNP ligand structure Cr (III) metal catalyst - Google Patents

Preparation method of PNP ligand structure Cr (III) metal catalyst Download PDF

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CN115124575B
CN115124575B CN202210726220.7A CN202210726220A CN115124575B CN 115124575 B CN115124575 B CN 115124575B CN 202210726220 A CN202210726220 A CN 202210726220A CN 115124575 B CN115124575 B CN 115124575B
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cyclopentylamine
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CN115124575A (en
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张宗飞
王淑敏
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China Wuhuan Engineering Co Ltd
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Abstract

The invention discloses a preparation method of a Cr (III) metal catalyst with a PNP ligand structure, which comprises the following steps: firstly) adding cyclopentylamine, chloro-diphenylphosphine and triethylamine solvent under nitrogen environment, and stirring and reacting at 0-30 ℃ to obtain triethylamine solution of N-cyclopentylamine-1, 1-diphenylphosphine ammonium; secondly), dropwise adding chlorinated dialkyl phosphine and a reaction catalyst into a triethylamine solution of N-cyclopentylamine-1, 1-diphenylphosphino ammonium to react under the condition of stirring at 0-30 ℃, and filtering and drying the mixture after the reaction is finished to obtain a dialkyl phosphino PNP ligand framework; thirdly), adding the dialkylphosphino PNP ligand skeleton and the Cr (III) metal compound into dichloromethane solution, stirring for reaction, recovering dichloromethane after the reaction is finished, filtering and drying to obtain the metal catalyst. The method is simple, the reaction condition is mild, the control is easy, the yield is high, and the catalytic activity of the prepared catalyst is high when the catalyst is used for ethylene oligomerization.

Description

Preparation method of PNP ligand structure Cr (III) metal catalyst
Technical Field
The invention belongs to the field of metal organic catalysts, and particularly relates to a preparation method of a Cr (III) metal catalyst with a PNP ligand structure.
Background
Alpha-olefin is an important organic chemical raw material and intermediate, can be used as a monomer for producing high-performance polyolefin, and can also be used for producing high-end lubricating oil, plasticizer, surfactant and the like.
At present, more than 80% of the global alpha-olefins are produced by adopting an ethylene oligomerization process, and the commercialized oligomerization process is basically mastered in an external enterprise. In the ethylene oligomerization catalytic reaction, the key factor affecting the catalytic reaction products is the catalyst, however, nickel-based catalysts, chromium-based catalysts and cobalt-based catalysts are monopolized. The start of China is late, and a plurality of scientific research institutions and enterprises are actively exploring and developing ethylene oligomerization catalysts at present.
Patent EP 0417477 reports ethylene trimerization catalyst systems consisting of 2, 5-dimethylpyrrole, chromium 2-ethylhexanoate, triethylaluminum and diethylaluminum chloride, and has successfully achieved commercial production of 1-hexene in Katal.
The China petrochemical institute uses chromium catalyst and triethylaluminum to develop 5000 ton/year industrial test in Daqing petrochemical industry, and establishes 2 ten thousand ton/year production device in Dushan petrochemical industry. The industrial conversion of producing hexene-1 in ethylene areas is completed in Yanshan by the medium petrochemical industry, and a production device of 5 ten thousand tons/year is built in the flourishing petrochemical industry.
CN 103724146a and CN 104961618A disclose methods for reducing polyethylene wax content in oligomerization products and improving linear alpha-olefin production by using ethers, ketones, lactones, heterocyclic compounds, organophosphine compounds, mono-or polycarboxylic acid compounds, silicon compounds containing silicon oxygen bonds, phenols containing hydroxyl groups, or the like as polyethylene wax inhibitors to adjust the iron and cobalt oligomerization catalyst systems. The method can obviously reduce the content of polyethylene wax under the condition of keeping high activity, but still has the defect of large consumption of the cocatalyst, and does not change the current situation of using expensive MAO as the cocatalyst. At present, no industrial production for preparing 1-octene by ethylene tetramerization is realized at home, and no particularly mature catalyst system exists.
EP 0608447A1 reports a chromium-based catalyst composition as a catalyst for oligomerization and/or copolymerization of ethylene, wherein a chromium-containing compound is used as one of the components of the catalyst composition; the pyrrole compound is used as the second component of the chromium-based catalyst composition; as a third component of the catalyst composition, a Lewis acid and/or a metal alkyl compound is used as an activator, and the halogen source can be inorganic halide or organic halide of various types, and the catalyst has high selectivity to 1-hexene but has low catalytic activity.
Meanwhile, the metal catalyst with PNP structure has lower temperature during synthesis, especially when butyl lithium is used for initiation, the temperature is required to be below-20 ℃ and is difficult to control. Liu Rui et al (Chin. J. Org. Chem.2017,37, 2315-2321) synthesized a PNP ligand metal catalyst under the action of butyllithium at-20 ℃. Butyl lithium is particularly active and unstable, and is easily decomposed at normal temperature, so that the synthesis reaction is difficult to control.
It can be seen that although various catalysts have been used in the ethylene oligomerization catalytic reaction in the prior art, the effect of these catalysts on the ethylene oligomerization catalytic reaction is still not ideal enough, so that it is still necessary to continuously research and explore more novel catalysts, which has a very important meaning for ethylene oligomerization.
Disclosure of Invention
The invention aims to provide a preparation method of a PNP ligand structure Cr (III) metal catalyst, which has the advantages of simple method, easy control, temperature reaction condition and high catalytic activity.
The preparation method of the PNP ligand structure Cr (III) metal catalyst comprises the following steps:
firstly) adding cyclopentylamine, chloro-diphenylphosphine and triethylamine solvent under nitrogen environment, and stirring and reacting at 0-30 ℃ to obtain triethylamine solution of N-cyclopentylamine-1, 1-diphenylphosphine ammonium;
secondly), dropwise adding chlorinated dialkyl phosphine and a reaction catalyst into a triethylamine solution of N-cyclopentylamine-1, 1-diphenylphosphino ammonium to react under the condition of stirring at 0-30 ℃, and filtering and drying the mixture after the reaction is finished to obtain a dialkyl phosphino PNP ligand framework;
thirdly), adding the dialkylphosphino PNP ligand skeleton and the Cr (III) metal compound into dichloromethane solution, stirring for reaction, recovering dichloromethane after the reaction is finished, filtering and drying to obtain the metal catalyst.
In the step 1), the stirring speed is 500-2000rpm, and the reaction time is 15-30min.
In the step 1), the mol ratio of the cyclopentylamine to the chlorodiphenylphosphine to the triethylamine solvent is 1:1 (1-3).
In the step 2), the reaction catalyst is a mixture of n-hexyllithium and micron-sized lithium iron phosphate.
In the step 2), the mixed molar ratio of the n-hexyllithium to the micron-sized lithium iron phosphate is (75-95) (25-5), and the total weight is 100 parts.
In the step 2), the micron-sized lithium iron phosphate is spherical, and the sphericity is more than or equal to 0.8 and less than 1.
In the step 2), the particle size of the micron-sized lithium iron phosphate is 0.1-100 mu m.
In the step 2), the addition amount of the dialkylphosphine is equal to the equimolar amount of the cyclopentylamine; the reaction catalyst is added in an amount of 5% -20% by mole of the cyclopentylamine.
In the step 2), the stirring speed is 500-2000rpm, and the reaction time is 30-60min.
The stirring speed is 500-2000rpm, the reaction time is 2-4h, and the reaction temperature is 0-30 ℃.
Based on the problem that when n-butyllithium pointed out in the background art is used as a reaction catalyst, the reaction temperature needs to be controlled below-20 ℃ because the n-butyllithium is very active and unstable, once the temperature is increased, the n-butyllithium is easy to decompose, the reaction is not easy to control, and the energy consumption is high under the low-temperature reaction. The inventor introduces a mixture of n-hexyllithium and micron-sized lithium iron phosphate as a reaction catalyst in the reaction of the step two), wherein n-hexyllithium has the characteristic of lower reaction activity than n-butyllithium, can be stably and difficultly decomposed at normal temperature, so that the reaction can be carried out at the temperature of 0-30 ℃, and the lithium iron phosphate has an orthorhombic olivine structure similar to the structure of the iron phosphate, lithium ions can be extracted/intercalated, and the crystal structure of the lithium iron phosphate is hardly rearranged, so that lithium ions in the lithium iron phosphate freely exist in a reaction system, inert iron elements can be activated under the combination of the lithium ions, the chromium and the iron elements, the energy required by the reaction can be reduced, the catalytic activity can be improved, the yield of the synthetic catalyst can be further improved, and various problems caused by the low-temperature reaction in the prior art are solved. And as the lithium iron phosphate is in a micron level, and further preferably, the particles of the lithium iron phosphate are approximately spherical, the particles are spontaneously converted into ultrathin nano sheets during the reaction, and a large amount of open space structures can be generated by the change, so that the catalytic reaction process is greatly accelerated. Here, the mixing ratio of the n-hexyllithium and the micron-sized lithium iron phosphate is preferably 75:25 to 95:5, and too high a mixing amount of the micron-sized lithium iron phosphate results in a higher content of inert iron elements, reduces the synergistic effect among lithium, chromium and iron elements, and too low a mixing amount results in a reduction of an open space structure and a prolonged catalytic reaction time.
The addition of the reaction catalyst is 5-20% of the N-cyclopentylamine-1, 1-diphenylphosphino ammonium, too much can lead to too fast reaction, extremely short operation time and difficult control, and simultaneously causes catalyst waste, too little can lead to slower reaction, long operation time or no catalysis.
Further, the step 2) and the step 3) adopt strong stirring, preferably the stirring speed is 500-2000rpm, and the high-speed stirring can enable the catalyst to be rapidly and uniformly distributed in the reaction system, so that the reaction is stably carried out, and the too low catalyst concentration can cause local reaction to be too fast.
In said step 3), the Cr (III) metal compound may be selected from CrCl 3 (THF) 3 ， CrBr 3 (THF) 3 ，CrF 3 (THF) 3 ，CrI 3 (THF) 3 。
The beneficial effects are that:
the method of the invention takes PNP structure as main framework, takes the mixture of N-hexyllithium and micron-sized lithium iron phosphate as the reference of catalytic reaction, can synthesize the catalyst under the condition of strong stirring at normal temperature, reduces energy consumption compared with low-temperature reaction, has easily controlled reaction process, mild reaction condition and higher yield, and the prepared catalyst has two coordination atoms of P and N, has high catalytic activity, and the catalytic activity can reach 99 multiplied by 10 6 g/(mol Cr.h), is especially suitable for ethylene oligomerization.
Detailed Description
Example 1
In the first step, 1mol of cyclopentylamine, 1mol of chlorodiphenylphosphine and 3mol of triethylamine are added into a reaction bottle under the nitrogen environment, and stirring is carried out for 30min at the temperature of 0 ℃ and the stirring speed of 1000rpm, and after the stirring is finished, a triethylamine solution of N-cyclopentylamine-1, 1-diphenylphosphine ammonium is obtained.
In a second step, 1mol of chlorodimethylphosphine and 0.05mol of a catalyst (a mixture of N-hexyllithium and lithium iron phosphate in a molar ratio of 75:25, wherein the sphericity of the lithium iron phosphate is 0.8 and the particle size is 0.1 um) were added dropwise to a triethylamine solution of N-cyclopentylamine-1, 1-diphenylphosphino ammonium at 0℃and a stirring rate of 2000rpm, and reacted for 60 minutes. After the reaction, the mixture was filtered to obtain a solid, which was dried to obtain a dimethylphosphinyl PNP ligand skeleton, and the dimethylphosphinyl PNP ligand skeleton was weighed to be 305.97g (or 0.92 mol) and represented by the structural formula I:
third, 0.5mol of the dimethylphosphinyl PNP ligand backbone and 0.5mol of CrCl are reacted at 0 DEG C 3 (THF) 3 Adding the catalyst into methylene dichloride solution, reacting for 4 hours at a stirring speed of 2000rpm, recovering the methylene dichloride therein by reduced pressure distillation after the reaction is finished, filtering and drying to obtain 214.57g of catalyst shown in a structural formula III (wherein R is methyl):
the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 88.3%.
Example 2
The triethylamine in example 1 was changed from 3mol to 2mol, and the other was unchanged, to obtain 219.2g of a final catalyst, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 90.2%.
Example 3
The triethylamine in example 1 was changed from 3mol to 1mol, and the other was unchanged, to obtain 210.2g of a final catalyst, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 86.5%.
Example 4
The yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 95.1% by changing the reaction temperature of the first step of example 1 to 15℃with the other conditions unchanged, 231.1g of the final catalyst.
Example 5
The reaction temperature of the first step in example 1 was changed to 30℃with the other being unchanged, 218.5g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 89.9%.
Example 6
The stirring rate 1000rpm in the first step of example 1 was changed to 500rpm, and the other was unchanged, 203.9g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 83.9%.
Example 7
The stirring rate 1000rpm in the first step of example 1 was changed to 2000rpm, and the other was unchanged, and 481.2g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 93.1%.
Example 8
The stirring rate 2000rpm in the second step of example 1 was changed to 1000rpm, and the other was unchanged, and 213.6g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 87.9%.
Example 9
The stirring rate 2000rpm in the second step of example 1 was changed to 500rpm, and the other was unchanged, 203.9g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 83.9%.
Example 10
The reaction time in the second step of example 1 was changed to 45min, and the other was unchanged, and 209.5g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 86.2%.
Example 11
The reaction time in the second step of example 1 was changed to 30min, and the other was unchanged, 204.8g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 84.3%.
Example 12
The yield of 226.9g of the final catalyst synthesized from cyclopentylamine was calculated to be about 87.6% by changing the chlorodimethylphosphine of the second step of example 1 to chlorodiethylphosphorus, and the other was unchanged. In the structural formula of the catalyst, R is ethyl.
Example 13
The yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 86.1% by changing the chlorodimethylphosphine of the second step of example 1 to diisopropylphosphorus chloride, leaving 233.3g of the final catalyst unchanged. In the structural formula of the catalyst, R is isopropyl.
Example 14
The yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 85.1% by changing the chlorodimethylphosphine of the second step of example 1 to di-t-butylphosphorus chloride, with the remainder unchanged, to 246.8g of the final catalyst. In the structural formula of the catalyst, R is tert-butyl.
Example 15
The catalyst amount in the second step of example 1 was changed from 0.05mol to 0.1mol, and the other was unchanged, 228.2g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 93.9%.
Example 16
The catalyst amount in the second step of example 1 was changed from 0.05mol to 0.2mol, and the other was unchanged, 228.7g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 94.1%.
Example 17
The mixture of n-hexyllithium and lithium iron phosphate in the second step of example 1 was changed to a mixture of n-hexyllithium and lithium iron phosphate in a molar ratio of 75:25, and the other was unchanged, and 229.1g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 94.3%.
Example 18
The mixture of n-hexyllithium and lithium iron phosphate in the second step of example 1 was changed to a mixture of n-hexyllithium and lithium iron phosphate in a molar ratio of 75:25, and the other was unchanged, 226.2g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 93.1%.
Example 19
The sphericity of the lithium iron phosphate of the second step in example 1 was changed to 0.9 while the other was unchanged, 230.9g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 95.0%.
Example 20
The sphericity of the lithium iron phosphate of the second step in example 1 was changed to 0.8 to 0.99, and the other was unchanged, and 231.3g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 95.2%.
Example 21
The yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 88.8% by changing the particle size of lithium iron phosphate of the second step of example 1 to 10um, with the other being unchanged, to 215.8g of the final catalyst.
Example 22
The yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 87.2% by changing the particle size of lithium iron phosphate of the second step of example 1 to 100. Mu.m, with the remainder being 211.9g of the final catalyst.
Example 23
CrCl of the third step in example 1 3 (THF) 3 Change to CrBr 3 (THF) 3 The yield of the final catalyst from cyclopentylamine was calculated to be about 82.6% for 256.5g of the final catalyst. The catalyst has the structural formula:
example 24
CrCl of the third step in example 1 3 (THF) 3 Change to CrI 3 (THF) 3 The yield of the final catalyst from cyclopentylamine was calculated to be about 80.9% with the other unchanged catalyst 308.2 g. The catalyst obtained has the following structural formula:
example 25
CrCl of the third step in example 1 3 (THF) 3 Change to CrF 3 (THF) 3 The yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 83.3% with the other unchanged catalyst 206.2 g. The catalyst obtained has the following structural formula:
example 26
The yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 90.2% by changing the reaction temperature of the third step of example 1 to 15℃at 0℃with the other being unchanged, 219.2g of the final catalyst.
Example 27
The reaction temperature in the third step of example 1 was changed to 30℃with the other conditions unchanged, 211.4g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 87.0%.
Example 28
The yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 84.5% by changing the stirring rate 2000rpm in the third step of example 1 to 1000rpm, and the other was unchanged, 205.3g of the final catalyst.
Example 29
The stirring rate 2000rpm in the third step of example 1 was changed to 500rpm, and the other was unchanged, and 200.2g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 82.4%.
Example 30
The reaction time of the third step in example 1 was changed to 4h for 3h, and the other was unchanged, 216.0g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 88.9%.
Example 31
The reaction time of the third step in example 1 was changed to 4h for 2h, and the other was unchanged, 212.9g of the final catalyst was obtained, and the yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 87.6%.
Comparative examples:
comparative example 1
When the mixture of n-hexyllithium and lithium iron phosphate in the molar ratio of 75:25 in example 1 is changed to n-butyllithium, the reaction temperature needs to be reduced below-20 ℃, the reaction is not changed, the reaction is difficult to control, 123.7g of the final catalyst is obtained, and the yield of the final catalyst synthesized from cyclopentylamine is calculated to be about 50.9%.
Comparative example 2
The yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 51.5% by changing the amount of lithium iron phosphate added in example 1 to 0, and the other was unchanged, to 125.1g of the final catalyst.
Comparative example 3
The yield of the final catalyst synthesized from cyclopentylamine was calculated to be about 50.6% by changing the particle size of lithium iron phosphate in example 1 to 1mm (millimeter scale) and the other to 122.9g of the final catalyst.
As can be seen from the above examples and comparative examples:
after the catalyst n-hexyllithium and lithium iron phosphate are changed into n-butyllithium according to the molar ratio of 75:25, the reaction cannot be carried out at normal temperature, the reaction can be carried out at-20 ℃, the reaction operation is relatively difficult, the yield is low, and the energy consumption of the example 1 is saved by about 13.4% compared with the comparative example 1 through simulation calculation.
When the addition amount of lithium iron phosphate is 0, the final yield is only 51.5% under the action of single normal lithium, and the yield is lower.
After the particle size of the added lithium iron phosphate is changed to millimeter level, the final yield is only 50.6%, and the yield is lower. It can be seen that millimeter-sized lithium iron phosphate has little effect in the reaction.
To characterize the activity of the catalyst, the above catalyst was applied to ethylene oligomerization.
Experimental example 1
The oligomerization reaction process is as follows: adding ethylene and a small amount of hydrogen into a reaction kettle, adding the catalyst synthesized in the embodiment 1, the catalyst promoter triethylaluminum and the organic solvent toluene into the reaction kettle, and performing oligomerization at 30 ℃ under 40bar for 200min.
Experimental example 2
The catalyst for synthesis of example 1 used in experimental example 1 was changed to the catalyst for synthesis of example 12, and the other was not changed.
Experimental example 3
The catalyst for synthesis of example 1 used in experimental example 1 was changed to the catalyst for synthesis of example 13, and the other was not changed.
Experimental example 4
The catalyst for synthesis of example 1 used in experimental example 1 was changed to the catalyst for synthesis of example 14, and the other was not changed.
Experimental example 5
The catalyst for synthesis of example 1 used in experimental example 1 was changed to the catalyst for synthesis of example 23, and the other was not changed.
Experimental example 6
The catalyst for synthesis of example 1 used in experimental example 1 was changed to the catalyst for synthesis of example 24, and the other was not changed.
Experimental example 7
The catalyst for synthesis of example 1 used in experimental example 1 was changed to the catalyst for synthesis of example 25, and the other was not changed.
Table 1 reports the catalyst activity and oligomerization results of some of the catalysts synthesized in the examples.
Table 1 shows the results of the catalytic reactions of experimental examples 1 to 7

Claims (9)

1. The preparation method of the PNP ligand structure Cr (III) metal catalyst is characterized by comprising the following steps:
firstly) adding cyclopentylamine, chloro-diphenyl phosphine and triethylamine solvent under the nitrogen environment, and stirring and reacting at 0-30 ℃ to obtain triethylamine solution of N-cyclopentyl-1, 1-diphenyl phosphine amine;
secondly), dropwise adding chlorinated dialkyl phosphine and a reaction catalyst into a triethylamine solution of N-cyclopentyl-1, 1-diphenylphosphinamine to react under the stirring condition at the temperature of 0-30 ℃, and filtering and drying the mixture after the reaction is finished to obtain a dialkyl phosphino PNP ligand framework; the reaction catalyst is a mixture of n-hexyllithium and micron-sized lithium iron phosphate;
thirdly), adding the dialkylphosphino PNP ligand skeleton and the Cr (III) metal compound into dichloromethane solution, stirring for reaction, recovering dichloromethane in the reaction after the reaction is finished, filtering and drying to obtain a metal catalyst; the Cr (III) metal compound is CrCl 3 (THF) 3 、CrBr 3 (THF) 3 、CrF 3 (THF) 3 、CrI 3 (THF) 3 One of them.
2. The process for preparing a Cr (III) metal catalyst having a PNP ligand structure according to claim 1, wherein in said step one), the stirring speed is 500 to 2000rpm and the reaction time is 15 to 30 minutes.
3. The method for preparing the metal catalyst with the PNP ligand structure Cr (III) according to claim 1 or 2, wherein in the first step), the molar ratio of cyclopentylamine, chlorodiphenylphosphine and triethylamine is 1:1 (1-3).
4. The process for producing a Cr (III) metal catalyst having a PNP ligand structure according to claim 1, wherein in said step two), the molar ratio of n-hexyllithium to micron-sized lithium iron phosphate is (75-95): 25-5, and the total is 100 parts.
5. The method for preparing a metal catalyst with a PNP ligand structure Cr (III) according to claim 1, wherein in the second step), the micron-sized lithium iron phosphate is spherical, and the sphericity is more than or equal to 0.8 and less than 1.
6. The method for preparing a metal catalyst of PNP ligand structure Cr (III) according to claim 1, wherein in said step two), said micron-sized lithium iron phosphate has a particle size of 0.1 to 100. Mu.m.
7. The process for preparing a metal catalyst of PNP ligand structure Cr (III) according to claim 1, 4, 5 or 6, wherein in said step two), said added amount of said chlorinated dialkylphosphine is an equimolar amount of said cyclopentylamine; the addition amount of the reaction catalyst is 5% -20% of the mole amount of the cyclopentylamine.
8. The process for preparing a Cr (III) metal catalyst having a PNP ligand structure according to claim 1, wherein in said step two), the stirring speed is 500 to 2000rpm and the reaction time is 30 to 60 minutes.
9. The process for preparing a Cr (III) metal catalyst having a PNP ligand structure according to claim 1 or 8, wherein in said step three), the stirring speed is 500 to 2000rpm, the reaction time is 2 to 4 hours, and the reaction temperature is 0 to 30 ℃.
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