CN103301874B - Method for improving selective hydrogenation ring opening of polycyclic aromatic hydrocarbon and catalyst composition thereof - Google Patents
Method for improving selective hydrogenation ring opening of polycyclic aromatic hydrocarbon and catalyst composition thereof Download PDFInfo
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Abstract
The invention discloses a method for improving the selective hydrogenation ring opening of polycyclic aromatic hydrocarbon and a catalyst composition thereof. The method uses a combined catalyst system and employs water as an additive. Specifically, the combined catalyst is a mixture of a solid acid loaded VIII group metal catalyst and a Mo-containing catalyst. The employment of the combined catalyst and the use of water as the additive significantly improve the yield of a selective ring opening product. Compared with the prior art, the combined catalyst disclosed in the invention has a plurality of active centers, the target product has high selectivity, and the catalyst has a simple preparation method and a low cost. The use of water as the additive significantly enhances the target product yield, and is green and controllable.
Description
Technical field
The present invention relates to a kind of method and the carbon monoxide-olefin polymeric thereof that improve polycyclic aromatic hydrocarbon selective hydrogenation open loop.
Background technology
Compare gasoline, diesel oil has higher energy and lower greenhouse gas emissions, and therefore, for the demand of environmental protection, the use amount of diesel oil increases sharply.But as the light cycle oil of diesel oil main source, its main component is polycyclic aromatic hydrocarbon, and these materials have very low Cetane number, and after polycyclic aromatic hydrocarbon being changed into alkylbenzene or alkyl cyclohexane, Cetane number reaches about 45, be just in time applicable to diesel engine.This conversion process is the selective hydrogenation ring-opening reaction of light cycle oil.
Add the arene content in Hydrogen Energy minimizing raw material, but the cycloalkane produced compares aromatic hydrocarbons, and raising is few.And normally used hydrocracking catalyst is generally the metal that acid carrier load has hydrogenation activity, therefore there is hydrogenation and open loop function, can by aromatic hydrocarbons open loop.But a large amount of low-boiling products can be produced, particularly some gaseous products, the yield of product liquid is reduced, and high cetane number product reduces.Therefore, high cetane number product be obtained, catalyst must be made to have hydrogenation and ring opening, and ring opening be moderate, ensure that liquid is received.
Selective hydrogenation ring-opening reaction is exactly a kind of method improving polycyclic aromatic hydrocarbon Cetane number, and it is selective is the product being mainly high cetane number in product, as alkyl cyclohexane, alkylbenzene etc.Desirable selective hydrogenation ring-opening reaction only carries out ring-opening reaction after being aromatic hydrogenation, can not produce Small molecular, not have carbon loss.
At present, researcher generally uses naphthalene, naphthane and decahydronaphthalene to make model reaction thing research selective hydrogenation ring-opening reaction.General use solid acid catalyst and bifunctional catalyst.Serious and the catalyst very easily inactivation of solid acid catalysis overreact cracking, therefore gained open loop contracting ring product is less, as [J.Catal., 200,34 (2001)].Bifunctional catalyst is acid carrier carried metal, the molecular sieve that the carrier adopted at present is mainly acid, and metal is divided into Rh, Ir, the noble metals such as Pt, as [Appl.Catal., A, 260,9 (2004), J.Catal., 278,253 (2011), J.Catal., 228,100 (2004), US 6,241,876 B1, US 6,683,020 B2 etc.], and Mo, the normal transition metals such as Ni, as [Appl.Catal., A, 403,36 (2011), J.Catal., 186,45 (1999), US5620590 etc.].The general activity of catalyst of carried noble metal is higher, but cost is higher, and not resistant to sulfur, and the catalyst cost of load normal transition metal is lower, and Sulfur tolerance is also relatively better, but corresponding activity is also low.The main difficulty of selective hydrogenation ring-opening reaction is mating of hydrogenation and cracking reaction.
US 3929618 has prepared the NaY type molecular sieve that a kind of nickel ion exchanges, then load Ni, W or V.Prepared catalyst has higher activity, particularly Ni-W-V/NiY for selective hydrogenation open loop, and be in the product of model thing with methyl naphthalene, the gross production rate of single aromatic rings product and decahydronaphthalene can reach 78%, and methyl naphthalene conversion ratio is up to 85%.For transition metal, this invention has reached very high activity, but has very large room for promotion, and includes decahydronaphthalene part during its calculation of yield.In addition, the method optimum temperature is 350-470 DEG C of scope, temperature required higher.
US 6241876 B1 has prepared a kind of efficient selective opening catalyst, the catalyst of the molecular sieve carried 8th race's noble metal of HY, wherein particularly Pt/USY, and such catalyst can improve the Cetane number of diesel oil at lower temperature.Although this catalyst also can remove the hetero atom in reaction mass, as N or S, its anti-hetero atom is limited in one's ability, and the preparation of carrier USY comparatively common molecular sieve complexity, and cost is higher.
US 6623626 has prepared the combination catalyst of group VIII metal and Pt or Pd, and this catalyst is very effective for the selective opening of cycloaliphatic ring alkane, and especially Ir and wherein Pt and Pd are as additive, can effectively catalysis hexatomic ring to pentacyclic isomerization reaction.But for the component containing aromatic hydrocarbons, need in advance through an aromatics saturation process.All contain aromatic component in most of fuel, therefore this invention needs to carry out in two steps for polycyclic aromatic hydrocarbon, complex process.
Appl.Catal., A, 257,340 (2008) catalyst reporting a kind of Si-Al molecular sieve load P d-Rh alloy are in the reaction of model thing with naphthalene, the productive rate of selective hydrogenation open-loop products can reach 47.9%, reaction condition is 300 DEG C, Hydrogen Vapor Pressure 6MPa, but in resistance to SO_2 test, the performance of this catalyst is poor, and after adding 100ppm dibenzo thiophene in system, open-loop products productive rate drops to 20%.
Summary of the invention
The object of this invention is to provide a kind of method and the carbon monoxide-olefin polymeric thereof that improve polycyclic aromatic hydrocarbon selective hydrogenation open loop.
Carbon monoxide-olefin polymeric provided by the invention, comprises solid acid supported V III metal oxide catalyst and contains Mo catalyst;
Wherein, in described solid acid supported V III metal oxide catalyst, described solid acid is acidic molecular sieve; Described acidic molecular sieve is selected from least one in HY acidic molecular sieve, USY acidic molecular sieve, ZSM acidic molecular sieve, BETA acidic molecular sieve and MCM-22 acidic molecular sieve, preferred HY acidic molecular sieve; Metallic element in described group VIII metal oxide is selected from least one in Ir, Pt, Ru, Pd and Rh, preferred Rh; The load quality percentage composition of described group VIII metal oxide in described solid acid supported V III metal oxide catalyst is 0.5-5%, preferably 2%;
The preparation of described HY molecular sieve, with reference to [J.Catal.100,228 (2004)], is obtained by NaY molecular sieve ion-exchange, 100g NaY is added 1L NH
4in Cl solution (120.5g/L), form suspension, magnetic agitation 2h, then by solid filtering, washing, obtains HY molecular sieve.
HY molecular sieve surface has B acid site, and after adding suitable quantity of water, the B acid site that surface can be promoted new generates.Water/HY mass ratio, in 0-40%, increases and the B acid site increase of generation with the water yield, and after increasing water addition further, the original acidic site of HY molecular sieve surface is capped, acid reduction.
Described is the bimetallic sulfide that Mo and transition metal form containing Mo catalyst; Described transition metal is selected from least one in Ni, Fe and Co, preferred Ni; The mass ratio of described Mo and described transition metal is 1: 0.5-2, is specially 2: 1,3: 2,1: 1,2: 3 or 1: 2, preferably 3: 2;
Described solid acid supported V III metal oxide catalyst and be 1: 0.1-1 containing the mass ratio of Mo catalyst, is specially 1: 0.1,1: 0.3,1: 0.5,1: 0.7,1: 1 or 1: 1.6, and preferably 1: 0.3.
The method of the described carbon monoxide-olefin polymeric of preparation provided by the invention, comprises the steps:
1) by after water-soluble for group VIII metal oxide precursor, add described solid acid and carry out incipient impregnation, then calcine after standing and drying, obtain described solid acid supported V III metal oxide catalyst;
2) Mo-transition metal alloy oxides and Cosan mixed in hydrogen atmosphere react, react complete obtain described containing Mo catalyst; Wherein, described transition metal is selected from least one in Ni, Fe and Co;
3) by described step 1) gained solid acid supported V III metal oxide catalyst and described step 2) gained mixes containing Mo catalyst, obtains described carbon monoxide-olefin polymeric.
The step 1 of said method) in, described group VIII metal oxide precursor is selected from least one in the halide of group VIII metal element, nitrate and sulfate; Described group VIII metal oxide precursor physical efficiency is water-soluble; Metallic element in described group VIII metal oxide precursor is selected from least one in Ir, Pt, Ru, Pd and Rh, preferred Rh;
In the water-soluble step of described group VIII metal oxide precursor, the mass ratio of described group VIII metal oxide precursor, water and described solid acid is 1: 0.5-100: 0.5-100, be specially 1: 92.3: 76.2,1: 50.7: 42.3,1: 23.5: 19.2,1: 12.5: 10.4 or 1: 0.94: 0.74, preferably 1: 23.5: 19.2 (corresponding metal simple-substance load quality percentage on solid acid is 0.5%-5%); The consumption of described water is the saturated water adsorptive value of described solid acid;
Described solid acid is in advance through vacuum drying treatment; This vacuum drying method is conventional method, as long as by the moisture removal in solid acid.
Described step 2) in, the mass ratio of described Mo-transition metal alloy oxides and Cosan is 1: 1-4, is specially 1: 1,1: 3 or 1: 4, preferably 1: 2; In described Mo-transition metal alloy oxides, the mass ratio of described Mo and transition metal is 1: 0.5-2, is specially 2: 1,3: 2,1: 1,2: 3 or 1: 2, preferably 3: 2; In described reactions steps, temperature is 250-360 DEG C, preferably 340 DEG C, and the time is 1-5 hour, preferably 4 hours;
The preparation method of described Mo-transition metal alloy oxides is sol-gal process, after specifically comprising the steps: the nitrate aqueous solution of transition metal and the aqueous solution of ammonium molybdate to mix according to the proportioning of Mo and transition metal, heat in 80 DEG C of waters bath with thermostatic control, stir, dropwise add citric acid solution, and stir in 80 DEG C of constant temperature, impel complex compound to be polymerized and generate gel, evaporate to dryness, obtain xerogel, be placed in Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, be cooled to room temperature, obtain described Mo-transition metal alloy oxides powder.
Described step 3) in, described solid acid supported V III metal oxide catalyst and be 1: 0.1-1 containing the mass ratio of Mo catalyst, is specially 1: 0.1,1: 0.3,1: 0.5,1: 0.7 or 1: 1, and preferably 1: 0.3.
The application of the carbon monoxide-olefin polymeric that the invention described above provides in polycyclic aromatic hydrocarbon hydrogenation ring-opening reaction, also belongs to protection scope of the present invention.
The method of polycyclic aromatic hydrocarbon hydrogenation provided by the invention open loop, comprises the steps: in hydrogen atmosphere, the mixing of polycyclic aromatic hydrocarbon, described carbon monoxide-olefin polymeric and water is reacted, reacts the complete hydrogenation open loop completing described polycyclic aromatic hydrocarbon.
In said method, described polycyclic aromatic hydrocarbon is selected from least one in naphthalene and naphthane, preferred naphthalene.
The mass ratio of described polycyclic aromatic hydrocarbon, described carbon monoxide-olefin polymeric is 6: 4-15, preferably 6: 9.5.
In described reactions steps, Hydrogen Vapor Pressure is 3-6MPa, and temperature is 250-360 DEG C, and the time is 1-4 hour.When temperature is higher, contribute to cracking reaction.But meanwhile, when temperature is higher, can cracking reaction be accelerated, and then generate many Small molecular products, and the condensation reaction of catalyst surface increases, generate green coke presoma.In order to control the side reaction that caused by high temperature and regulate the acidity of catalyst, water is added to control reaction in reaction, hydrone is in catalyst surface and reactant molecule competitive Adsorption, condensation reaction can be suppressed, and after hydrone covers on partially acidic site, can prevent cracking reaction from occurring further.
Inquire into as follows to Related Mechanism of the present invention: find through research, in naphthalene selective hydrogenation ring-opening reaction, the principal element affecting open-loop products productive rate comprises the following aspects, one is mainly comprise hydrogenation due to course of reaction and cracking two class is reacted, if hydrogenation activity is excessively strong, then the corresponding meeting of cracking reaction is suppressed, on the other hand, if the bronsted acid of catalyst system is comparatively strong, then lytic activity is excessively strong, can cross cracking and generate Small molecular and high molecular weight product even coke.Two is that the impact of temperature on reaction is larger, and according to thermodynamic study, lower temperature is conducive to hydrogenation reaction, and higher temperature is conducive to cracking.Under the condition that temperature is lower, mainly generate hydrogenation products, under the condition that temperature is higher, cracking is serious excessively.Therefore, selecting a kind of hydrogenation to mate suitable catalyst with cracking activity is the key obtaining high open-loop products productive rate.In the present invention, by Mo-Ni catalyst and Rh
2o
3after/HY mixing, the productive rate of open-loop products significantly improves, and Mo-Ni catalyst forms bronsted acid site in hydrogen, improves the acidity of catalyst system.After adding suitable quantity of water, on the one hand with molecular sieve carrier effect, generate new bronsted acid site, on the other hand, suppress reactant to generate high molecular weight product in catalyst surface condensation reaction, the productive rate of open-loop products improves further.
The present invention compared with prior art has the following advantages: 1, the present invention is at Rh
2o
3mix Mo-Ni catalyst in/HY, improve the acidity of catalyst system.And reduce the cost of catalyst, and preparation is simple.2, use water as additive in the present invention, the productive rate of target product can be significantly improved, again environmental protection, easily regulate and control.
Accompanying drawing explanation
Fig. 1 is the GC-MS spectrogram of embodiment 18 gained naphthalene selective opening product.
Fig. 2 is the result of the comparison of embodiment 18 gained naphthalene selective opening product and NIST standard gallery.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.Following described two kinds of naphthalenes used and naphthane are all purchased from Shantou Xi Long chemical company (GuangZhou, China), and Cosan, rhodium chloride and normal heptane are purchased from Beijing chemical reagents corporation, and it is pure that all medicines are analysis.HY molecular sieve is bought from Taixing, Zibo chemical company (Shandong Province of China).
Embodiment one: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve is placed in vacuum drying 10 hours, by 0.0051g RhCl
33H
2o is dissolved in 0.12g distilled water, adds the good HY molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12 hours, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ HY.
By 6.34g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take 5mg Rh
2o
3/ HY and Mo-Ni oxide 1.5mg, Cosan 3mg, after physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment two: the preparation of carbon monoxide-olefin polymeric
0.098g ZSM molecular sieve is placed in vacuum drying 10h, by 0.0051g RhCl
33H
2o is dissolved in 0.12g distilled water, adds the good ZSM molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ ZSM.
By 6.34g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take 5mg Rh
2o
3/ ZSM and Mo-Ni oxide 1.5mg, Cosan 3mg, after physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment three: the preparation of carbon monoxide-olefin polymeric
0.098g BETA molecular sieve is placed in vacuum drying 10h, by 0.0051g RhCl
33H
2o is dissolved in 0.12g distilled water, adds the good BETA molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ BETA.
By 6.34g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take 5mg Rh
2o
3/ BETA and Mo-Ni oxide 1.5mg, Cosan 3mg, after physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment four: the preparation of carbon monoxide-olefin polymeric
0.098g USY molecular sieve is placed in vacuum drying 10h, by 0.0051g RhCl
33H
2o is dissolved in 0.12g distilled water, adds the good USY molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ USY.
By 6.34g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take 5mg Rh
2o
3/ USY and Mo-Ni oxide 1.5mg, Cosan 3mg, after physical mixed, namely obtain carbon monoxide-olefin polymeric.
Embodiment five: the preparation of carbon monoxide-olefin polymeric
0.098g MCM-22 molecular sieve is placed in vacuum drying 10h, by 0.0051g RhCl
33H
2o is dissolved in 0.12g distilled water, adds the good MCM-22 molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ MCM-22.
By 6.34g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take 5mg Rh
2o
3/ MCM-22 and Mo-Ni oxide 1.5mg, Cosan 3mg, after physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment six: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve is placed in vacuum drying 10h, by 0.0037g IrCl
33H
2o is dissolved in 0.12g distilled water, adds the good HY molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Ir
2o
3/ HY.
By 6.34g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take 5mg Ir
2o
3/ HY and Mo-Ni oxide 1.5mg, Cosan 3mg, after physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment seven: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve is placed in vacuum drying 10h, by 0.0033g PdCl
2be dissolved in 0.12g distilled water, add the good HY molecular sieve of vacuum drying after dissolving completely, after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains PdO/HY.
By 6.34g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take 5mg PdO/HY and Mo-Ni oxide 1.5mg, Cosan 3mg, after physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment eight: the preparation of carbon monoxide-olefin polymeric
0.099g HY molecular sieve is placed in vacuum drying 10h, by 0.0013g RhCl
3h
2o is dissolved in 0.12g distilled water, adds the good HY molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ HY.
By 6.34g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take 5mg Rh
2o
3/ HY and Mo-Ni oxide 1.5mg, Cosan 3mg, after physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment nine: the preparation of carbon monoxide-olefin polymeric
0.095g HY molecular sieve is placed in vacuum drying 10h, by 0.128g RhCl
33H
2o is dissolved in 0.12g distilled water, adds the good HY molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ HY.
By 6.34g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take 5mg Rh
2o
3/ HY and Mo-Ni oxide 1.5mg, Cosan 3mg, after physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment ten: the preparation of carbon monoxide-olefin polymeric
By 1.1g 0.9g Fe (NO
3)
39H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of finite concentration, volume, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-iron oxide powder.
0.098g HY molecular sieve is placed in vacuum drying 10h, by 0.0051g RhCl
33H
2o is dissolved in 0.12g distilled water, adds the good HY molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ HY.Then 1.5mg is got, with 3mg Cosan, 5mg Rh
2o
3after/HY physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 11: the preparation of carbon monoxide-olefin polymeric
By 1.1g Co (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then mixes (transition metal/Mo=2/3), and in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-cobalt/cobalt oxide powder.
0.098g HY molecular sieve is placed in vacuum drying 10h, by 0.0051g RhCl
3h
2o is dissolved in 0.12g distilled water, adds the good HY molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ HY.Then 1.5mg is got, with 3mg Cosan, 5mg Rh
2o
3after/HY physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 12: the preparation of carbon monoxide-olefin polymeric
By 4.78g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=1/2) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.
0.098g HY molecular sieve is placed in vacuum drying 10h, by 0.0051g RhCl
33H
2o is dissolved in 0.12g distilled water, adds the good HY molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ HY.Then 1.5mg is got, with 3mg Cosan, 5mg Rh
2o
3after/HY physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 13: the preparation of carbon monoxide-olefin polymeric
By 19.13g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then mixes (transition metal/Mo=2/1), and in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-cobalt/cobalt oxide powder.
0.098g HY molecular sieve is placed in vacuum drying 10h, by 0.0051g RhCl
33H
2o is dissolved in 0.12g distilled water, adds the good HY molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ HY.Then 1.5mg molybdenum-cobalt/cobalt oxide powder is got, with 3mg Cosan, 5mg Rh
2o
3after/HY physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 14: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve is placed in vacuum drying 10h, by 0.0051g RhCl
33H
2o is dissolved in 0.12g distilled water, adds the good HY molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ HY.
By 6.34g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take 5.9mg Rh
2o
3/ HY and Mo-Ni oxide 0.6mg, Cosan 1.2mg, i.e. Rh
2o
3/ HY: Mo-Ni oxide=1: 0.1.After physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 15: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve is placed in vacuum drying 10h, by 0.0051g RhCl
33H
2o is dissolved in 0.12g distilled water, adds the good HY molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ HY.
By 6.34g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take 2.5mg Rh
2o
3/ HY and Mo-Ni oxide 4mg, Cosan 8mg, i.e. Rh
2o
3/ HY: Mo-Ni oxide=1: 1.6.After physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 16: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve is placed in vacuum drying 10h, by 0.0051g RhCl
33H
2o is dissolved in 0.12g distilled water, adds the good HY molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ HY.
By 6.34g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take 5mg Rh
2o
3/ HY and Mo-Ni oxide 1.5mg, Cosan 1.5mg, i.e. Mo-Ni oxide: Cosan (mass ratio)=1: 1.After physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 17: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve is placed in vacuum drying 10h, by 0.0051g RhCl
33H
2o is dissolved in 0.12g distilled water, adds the good HY molecular sieve of vacuum drying after dissolving completely, and after incipient impregnation, leave standstill 12h, being placed in Muffle furnace of 100 DEG C of dryings is calcined, and calcination condition is: 5 DEG C/min is warming up to 550 DEG C, and then constant temperature 3h, obtains Rh
2o
3/ HY.
By 6.34g Ni (NO
3)
26H
2o is dissolved in wiring solution-forming in 5ml water, by 1g (NH
4)
6mo
7o
244H
2o is dissolved in wiring solution-forming in 5ml water, then (transition metal/Mo mol ratio=2/3) is mixed, in 80 DEG C of waters bath with thermostatic control, heat, stir, dropwise add the citric acid solution of 1g/ml, solution stirs in 80 DEG C of constant temperature, impels complex compound to be polymerized and generates gel.Then evaporate to dryness, obtains xerogel.Be placed on Muffle furnace Program and be warming up to 500 DEG C, constant temperature 4 hours, is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take 5mg Rh
2o
3/ HY and Mo-Ni oxide 1.5mg, Cosan 6mg, i.e. Mo-Ni oxide: Cosan (mass ratio)=1: 4.After physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 18:
By 6mg naphthalene, catalyst 9.5mg prepared by embodiment one, 2mg water adds in autoclave, 5MPa hydrogen is passed into after sealing, reacting furnace temperature is controlled at 340 DEG C simultaneously, reactor is put into after temperature constant, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, concrete testing conditions is as follows: instrument is SHIMADZU GCMS-QP2010 gas chromatograph-mass spectrometer, chromatographic condition is: chromatographic column model: DB-5ms 30m0.25mm, column temperature condition is: 50 DEG C keep 2 minutes, 250 DEG C are warming up to 10 DEG C/min, keep 30 minutes, split ratio: 10: 1, injector temperature: 250 DEG C, Mass Spectrometry Conditions is: ion source temperature: 200 DEG C, electron energy 70eV, and sweep limits: 20-650m/z, acquired results is shown in Fig. 1 and table 1.
Table 1 gas chromatography mass spectrometry goes out peak report
By the comparison with NIST standard gallery, the most probable structure that in analysis diagram 1, each peak is corresponding, as shown in Figure 2.From Fig. 1 and Fig. 2, be numbered the equal corresponding open-loop products in peak of 1-29,31-33, be mainly alkyl naphthene and alkyl vinyl compound, be numbered the corresponding hydrogenation products trans-decalin in peak of 30, be numbered the corresponding hydrogenation products cis-decaline in 34 peaks, place, be numbered the corresponding high molecular weight product in peak of 35, be mainly Fluhyzon.Calculating open-loop products productive rate is 63.1%.
Embodiment 19:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment two is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 22.5%.
Embodiment 20:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment three is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 31.7%.
Embodiment 21:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment four is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 42.2%.
Embodiment 22:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment five is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 37.9%.
Embodiment 23:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment six is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 60.9%.
Embodiment 24:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment seven is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 40.4%.
Embodiment 25:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment eight is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 45.6%.
Embodiment 26:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment nine is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 36.8%.
Embodiment 27:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment ten is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 56.3%.
Embodiment 28:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment 11 is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 50.7%.
Embodiment 29:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment 12 is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 56.9%.
Embodiment 30:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment 13 is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 51.4%.
Embodiment 31:
Catalyst 7.7mg, 2mg water prepared by 6mg naphthalene, embodiment 14 is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 51.5%.
Embodiment 32:
Catalyst 14.5mg, 2mg water prepared by 6mg naphthalene, embodiment 15 is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 41.3%.
Embodiment 33:
Catalyst 8mg, 2mg water prepared by 6mg naphthalene, embodiment 16 is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 53.6%.
Embodiment 34:
Catalyst 12.5mg, 2mg water prepared by 6mg naphthalene, embodiment 17 is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 32.3%.
Embodiment 35:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment one is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 1h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 2.9%.
Embodiment 36:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment one is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 2h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 7.98%.
Embodiment 37:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment one is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 3h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 29.49%.
Embodiment 38:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthalene, embodiment one is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 5h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 47.44%.
Embodiment 39:
Catalyst 9.5mg, 2mg water prepared by 6mg naphthane, embodiment one is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 72.34%.
Embodiment 40:
Catalyst 15mg, 2mg water prepared by 6mg naphthalene, embodiment one is added in autoclave, pass into 5MPa hydrogen after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 5h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, each product of gained and Fig. 1 and 2 are without substantive difference, and only the peak area of each product is slightly different.Calculating open-loop products productive rate is 42.64%.
Embodiment 41:
Catalyst 4mg, 2mg water prepared by 6mg naphthalene, embodiment one is added in autoclave, 5MPa hydrogen is passed into after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 5h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, calculating open-loop products productive rate is 47.44%.
Embodiment 42:
By 6mg naphthalene, 9mg Rh
2o
3/ HY, 2mg water add in reactor, 5MPa hydrogen is passed into after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, obtain product and the results are shown in Table 1.
Embodiment 43:
6mg naphthalene, 1.5mg Mo-Ni, 3mg Cosan, 5mg HY, 2mg water are added in reactor, 5MPa hydrogen is passed into after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, obtain product and the results are shown in Table 2.
Embodiment 44:
By 6mg naphthalene, 6mg Rh
2o
3/ HY, 3mg Cosan, 2mg water add in reactor, 5MPa hydrogen is passed into after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, obtain product and the results are shown in Table 2.
Embodiment 45:
6mg naphthalene, 3mg Mo-Ni, 6mg Cosan, 2mg water are added in reactor, 5MPa hydrogen is passed into after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, obtain product and the results are shown in Table 2.
Embodiment 46:
By 6mg naphthalene, 4.5mg Mo-Ni, 5mg Rh
2o
3/ HY, 2mg water add in reactor, 5MPa hydrogen is passed into after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, obtain product and the results are shown in Table 2.
Embodiment 47:
By 6mg naphthalene, 1.5mg Mo-Ni, 3mg Cosan, 5mg Rh
2o
3/ HY, 2mg water add in reactor, 5MPa hydrogen is passed into after sealing, reacting furnace temperature is controlled, at 340 DEG C, after temperature constant, to put into reactor simultaneously, start timing, after reaction 4h, use washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, acquired results is in table 2.
Table 2, different catalysts component are on the impact of naphthalene selective hydrogenation ring-opening reaction
In table 2, open-loop products is mainly alkyl cyclohexane and alkyl cyclohexene, and high molecular weight product is mainly Fluhyzon, and hydrogenation products is mainly trans-decahydronaphthalene and cis-decahydronaphthalene.
Embodiment 42-47 describes the effect of combination catalyst different component catalysis naphthalene selective hydrogenation ring-opening reaction, and when Rh catalyst and Mo-Ni catalyst are used alone, open-loop products productive rate is not high, as Rh
2o
3/ HY catalytic reaction gained open-loop products only has 26.3%, Mo-Ni+HY then lower, is 11.6%.After adding sulphur, the productive rate of two kinds of catalyst gained open-loop products all remains on about 28%.After two kinds of catalyst combination use, open-loop products productive rate obviously increases, and continues to increase after adding sulphur.
Embodiment 48:
By 6mg naphthalene, 5mg Rh
2o
3/ HY, 1.5mg Mo-Ni, 3mg Cosan add in reactor, pass into 5MPa hydrogen, and temperature controls at 340 DEG C, and after reaction 4h, use washed with heptane reactor, add biphenyl as interior mark, adopt gas chromatographic analysis, acquired results is in table 3.
Embodiment 49:
By 6mg naphthalene, 5mg Rh
2o
3/ HY, 1.5mg Mo-Ni, 3mg Cosan, 6mg water add in reactor, pass into 5MPa hydrogen, and temperature controls at 340 DEG C, and after reaction 4h, use washed with heptane reactor, add biphenyl as interior mark, adopt gas chromatographic analysis, acquired results is in table 3.
Embodiment 50:
By 6mg naphthalene, 5mg Rh
2o
3/ HY, 1.5mg Mo-Ni, 3mg Cosan, 10mg water add in reactor, pass into 5MPa hydrogen, and temperature controls at 340 DEG C, and after reaction 4h, use washed with heptane reactor, add biphenyl as interior mark, adopt gas chromatographic analysis, acquired results is in table 3.
Embodiment 51:
By 6mg naphthalene, 5mg Rh
2o
3/ HY, 1.5mg Mo-Ni, 3mg Cosan, 50mg water add in reactor, pass into 5MPa hydrogen, and temperature controls at 340 DEG C, and after reaction 4h, use washed with heptane reactor, add biphenyl as interior mark, adopt gas chromatographic analysis, acquired results is in table 3.
Embodiment 52:
By 6mg naphthalene, 5mg Rh
2o
3/ HY, 1.5mg Mo-Ni, 3mg Cosan, 100mg water add in reactor, pass into 5MPa hydrogen, and temperature controls at 340 DEG C, and after reaction 4h, use washed with heptane reactor, add biphenyl as interior mark, adopt gas chromatographic analysis, acquired results is in table 3.
Embodiment 53:
By 6mg naphthalene, 5mg Rh
2o
3/ HY, 1.5mg Mo-Ni, 3mg Cosan, 400mg water add in reactor, pass into 5MPa hydrogen, and temperature controls at 340 DEG C, and after reaction 4h, use washed with heptane reactor, add biphenyl as interior mark, adopt gas chromatographic analysis, acquired results is in table 3.
Table 3, the water yield are on the impact of naphthalene selective hydrogenation ring-opening reaction
In table 3, open-loop products is mainly alkyl cyclohexane and alkyl cyclohexene, and high molecular weight product is mainly Fluhyzon, and hydrogenation products is mainly trans-decahydronaphthalene and cis-decahydronaphthalene.
Embodiment 48-53 is the impact of different water addition on reaction, and a small amount of water has facilitation for selective opening reaction, and with the increase of rate of water added, ring-opening reaction is first suppressed, and then hydrogenation sites is also capped, and hydrogenation reaction is suppressed.
Claims (9)
1. a carbon monoxide-olefin polymeric, comprises solid acid supported V III metal oxide catalyst and contains Mo catalyst;
Wherein, in described solid acid supported V III metal oxide catalyst, described solid acid is acidic molecular sieve;
Metallic element in described group VIII metal oxide is selected from least one in Ir, Pt, Ru, Pd and Rh;
The load quality percentage composition of described group VIII metal oxide in described solid acid supported V III metal oxide catalyst is 0.5-5%;
Described is the bimetallic sulfide that Mo and transition metal form containing Mo catalyst; Described transition metal is selected from least one in Ni, Fe and Co; The mass ratio of described Mo and described transition metal is 1:0.5-2;
Described solid acid supported V III metal oxide catalyst and the mass ratio containing Mo catalyst are 1:0.1-1;
Described acidic molecular sieve is selected from least one in HY acidic molecular sieve, USY acidic molecular sieve, ZSM acidic molecular sieve, BETA acidic molecular sieve and MCM-22 acidic molecular sieve.
2. carbon monoxide-olefin polymeric according to claim 1, is characterized in that: described acidic molecular sieve is HY acidic molecular sieve;
Metallic element in described group VIII metal oxide is Rh;
The load quality percentage composition of described group VIII metal oxide in described solid acid supported V III metal oxide catalyst is 2%;
Described containing in Mo catalyst, described transition metal is Ni; The mass ratio of described Mo and described transition metal is 3:2;
Described solid acid supported V III metal oxide catalyst and the mass ratio containing Mo catalyst are 1:0.3.
3. the application of carbon monoxide-olefin polymeric described in claim 1 or 2 in polycyclic aromatic hydrocarbon hydrogenation ring-opening reaction.
4. a method for polycyclic aromatic hydrocarbon hydrogenation open loop, comprises the steps: in hydrogen atmosphere, carbon monoxide-olefin polymeric described in polycyclic aromatic hydrocarbon, claim 1 or 2 and water mixing is reacted, reacts the complete hydrogenation open loop completing described polycyclic aromatic hydrocarbon.
5. method according to claim 4, is characterized in that: described polycyclic aromatic hydrocarbon is selected from least one in naphthalene and naphthane.
6. method according to claim 5, is characterized in that: described polycyclic aromatic hydrocarbon is naphthalene.
7. method according to claim 4, is characterized in that: described in described polycyclic aromatic hydrocarbon, claim 1 or 2, the mass ratio of carbon monoxide-olefin polymeric and water is 6:4-15.
8. method according to claim 7, is characterized in that: described in described polycyclic aromatic hydrocarbon, claim 1 or 2, the mass ratio of carbon monoxide-olefin polymeric and water is 6:9.5.
9., according to the arbitrary described method of claim 4-8, it is characterized in that: in described reactions steps, Hydrogen Vapor Pressure is 3-6MPa, and temperature is 250-360 DEG C, and the time is 1-4 hour.
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