CN103301874A - 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
- Publication number
- CN103301874A CN103301874A CN2012100636111A CN201210063611A CN103301874A CN 103301874 A CN103301874 A CN 103301874A CN 2012100636111 A CN2012100636111 A CN 2012100636111A CN 201210063611 A CN201210063611 A CN 201210063611A CN 103301874 A CN103301874 A CN 103301874A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- water
- metal oxide
- group viii
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 24
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 21
- 238000007142 ring opening reaction Methods 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000011973 solid acid Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 94
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 239000002808 molecular sieve Substances 0.000 claims description 62
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 62
- 229910052739 hydrogen Inorganic materials 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 45
- 229910052723 transition metal Inorganic materials 0.000 claims description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 36
- 150000003624 transition metals Chemical class 0.000 claims description 33
- 229910044991 metal oxide Inorganic materials 0.000 claims description 28
- 150000004706 metal oxides Chemical class 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 19
- 238000005470 impregnation Methods 0.000 claims description 19
- 230000002378 acidificating effect Effects 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229910002064 alloy oxide Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000012702 metal oxide precursor Substances 0.000 claims 4
- 238000010521 absorption reaction Methods 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 23
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 73
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 72
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 54
- 239000010948 rhodium Substances 0.000 description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 44
- 229910052799 carbon Inorganic materials 0.000 description 44
- 239000007789 gas Substances 0.000 description 37
- 150000002431 hydrogen Chemical class 0.000 description 37
- 235000010290 biphenyl Nutrition 0.000 description 36
- 239000004305 biphenyl Substances 0.000 description 36
- 238000004587 chromatography analysis Methods 0.000 description 36
- 239000000243 solution Substances 0.000 description 36
- 238000003756 stirring Methods 0.000 description 36
- 238000001291 vacuum drying Methods 0.000 description 36
- 238000010792 warming Methods 0.000 description 36
- 229910017318 Mo—Ni Inorganic materials 0.000 description 32
- 238000007789 sealing Methods 0.000 description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- 239000003643 water by type Substances 0.000 description 18
- 206010013786 Dry skin Diseases 0.000 description 17
- 239000012153 distilled water Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 16
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 15
- CIHYROJTBKFOPR-UHFFFAOYSA-N nickel;oxomolybdenum Chemical compound [Ni].[Mo]=O CIHYROJTBKFOPR-UHFFFAOYSA-N 0.000 description 14
- 238000005303 weighing Methods 0.000 description 13
- 238000005336 cracking Methods 0.000 description 11
- -1 alkyl cyclohexane Chemical compound 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 7
- 230000000875 corresponding effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007848 Bronsted acid Substances 0.000 description 3
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- NNBZCPXTIHJBJL-MGCOHNPYSA-N trans-decalin Chemical compound C1CCC[C@@H]2CCCC[C@H]21 NNBZCPXTIHJBJL-MGCOHNPYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种提高多环芳烃选择性加氢开环的方法及其催化剂组合物。该方法使用组合催化剂体系以及水作为添加剂。其中，组合催化剂为固体酸负载VIII族金属催化剂与含Mo催化剂的混合物。组合催化剂的使用以及水作为添加剂的作用，显著提高了选择性开环产物的产率。与现有技术相比，本发明所述组合催化剂具有多个活性中心，目标产物选择性高，催化剂制备方法简单，而且成本较低，水作为添加剂，显著提高目标产物产率，而且绿色可控。The invention discloses a method for improving selective hydrogenation and ring opening of polycyclic aromatic hydrocarbons and a catalyst composition thereof. The method uses a combined catalyst system with water as an additive. Wherein, the combined catalyst is a mixture of a solid acid supported Group VIII metal catalyst and a Mo-containing catalyst. The use of combined catalysts and the role of water as an additive significantly increased the yield of selective ring-opened products. Compared with the prior art, the combined catalyst of the present invention has multiple active centers, the selectivity of the target product is high, the preparation method of the catalyst is simple, and the cost is low. Water is used as an additive to significantly increase the yield of the target product, and it is green and controllable .
Description
Technical field
The present invention relates to a kind of method and carbon monoxide-olefin polymeric thereof that improves 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, polycyclic aromatic hydrocarbon is changed into alkylbenzene or alkyl cyclohexane after Cetane number reach about 45, just in time be fit to diesel engine.This conversion process is the selective hydrogenation ring-opening reaction of light cycle oil.
Add the arene content in the Hydrogen Energy minimizing raw material, raising is few but the cycloalkane that produces is compared aromatic hydrocarbons.And normally used hydrocracking catalyst is generally the metal that the acid carrier load has hydrogenation activity, therefore has hydrogenation and open loop function, can be with the aromatic hydrocarbons open loop.But can produce a large amount of low-boiling products, particularly some gaseous products make the yield of product liquid reduce, and the high cetane number product reduce.Therefore, obtain the high cetane number product, must make catalyst have hydrogenation and ring opening, and ring opening be moderate, guarantee the liquid receipts.
The selective hydrogenation ring-opening reaction is exactly a kind of method that improves the polycyclic aromatic hydrocarbon Cetane number, and it selectively is to be mainly in the product product of high cetane number, as alkyl cyclohexane, alkylbenzene etc.Desirable selective hydrogenation ring-opening reaction is that aromatic hydrogenation only carries out ring-opening reaction afterwards, can not produce little molecule, does not have carbon loss.
At present, the researcher generally uses naphthalene, naphthane and decahydronaphthalene to make model reaction thing research selective hydrogenation ring-opening reaction.General solid acid catalyst and the bifunctional catalyst of using.Serious and the catalyst of solid acid catalysis overreact cracking is inactivation very easily, so gained open loop contracting ring product is less, as [J.Catal., 200,34 (2001)].Bifunctional catalyst is the acid carrier carried metal, and the carrier that adopts mainly is acid molecular sieve at present, and metal is divided into Rh, Ir, and noble metals such as Pt are 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, normal transition metals such as Ni are as [Appl.Catal., A, 403,36 (2011), J.Catal., 186,45 (1999), US5620590 etc.].The catalyst of carried noble metal is general active higher, but cost is higher, and not anti-sulphur, and the catalyst cost of load normal transition metal is lower, and anti-sulphur is also better relatively, but corresponding activity is also low.The main difficulty of selective hydrogenation ring-opening reaction is the coupling of hydrogenation and cracking reaction.
US 3929618 has prepared a kind of NaY type molecular sieve of nickel ion exchange, load Ni, W or V then.Prepared catalyst has higher activity, particularly Ni-W-V/NiY for the selective hydrogenation open loop, is in the product of model thing with the methyl naphthalene, and the gross production rate of single aromatic rings product and decahydronaphthalene can reach 78%, and the methyl naphthalene conversion ratio is up to 85%.For transition metal, this invention has reached very high activity, but very big room for promotion is arranged, and has comprised the decahydronaphthalene part during its calculation of yield.In addition, this method optimum temperature is 350-470 ℃ of scope, and is temperature required higher.
US 6241876 B1 have prepared a kind of catalyst of selective opening efficiently, the catalyst of molecular sieve carried the 8th family's noble metal of HY, and Pt/USY particularly wherein, such catalyst can improve the Cetane number of diesel oil at lower temperature.Though this catalyst also can remove the hetero atom in the reaction mass, as N or S, its anti-hetero atom is limited in one's ability, and the more common molecular sieve complexity of the preparation of carrier USY, and cost is higher.
US 6623626 has prepared the combination catalyst of VIII family metal and Pt or Pd, and this catalyst is very effective for the selective opening of cycloaliphatic ring alkane, and especially Ir is with wherein Pt and Pd are as additive, and effectively the catalysis hexatomic ring is to pentacyclic isomerization reaction.But for the component that contains aromatic hydrocarbons, need in advance through an aromatics saturation process.All contain aromatic component in most of fuel, so this invention need be carried out complex process in two steps for polycyclic aromatic hydrocarbon.
Appl.Catal., A, 257,340 (2008) have reported a kind of catalyst of Si-Al molecular sieve load P d-Rh alloy, are in the reaction of model thing with the naphthalene, the productive rate of selective hydrogenation open-loop products can reach 47.9%, reaction condition is 300 ℃, Hydrogen Vapor Pressure 6MPa, but in anti-sulphur property testing, the performance of this catalyst is relatively poor, add the 100ppm dibenzo thiophene in the system after the open-loop products productive rate drop to 20%.
Summary of the invention
The purpose of this invention is to provide a kind of method and carbon monoxide-olefin polymeric thereof that improves polycyclic aromatic hydrocarbon selective hydrogenation open loop.
Carbon monoxide-olefin polymeric provided by the invention comprises solid acid supported V III family metal oxide catalyst and contains the Mo catalyst;
Wherein, in the described solid acid supported V III family metal oxide catalyst, described solid acid is acidic molecular sieve; Described acidic molecular sieve is selected from least a in HY acidic molecular sieve, USY acidic molecular sieve, ZSM acidic molecular sieve, BETA acidic molecular sieve and the MCM-22 acidic molecular sieve, preferred HY acidic molecular sieve; Metallic element in the described VIII family metal oxide is selected from least a among Ir, Pt, Ru, Pd and the Rh, preferred Rh; The load quality percentage composition of described VIII family metal oxide in described solid acid supported V III family metal oxide catalyst is 0.5-5%, preferred 2%;
The preparation of described HY molecular sieve is made by the ion-exchange of NaY molecular sieve with reference to [J.Catal.100,228 (2004)], and 100g NaY is added 1L NH
4In the Cl solution (120.5g/L), form suspension, magnetic agitation 2h, then with solid filtering, washing namely gets the HY molecular sieve.
HY molecular sieve surface has B acid site, and after adding suitable quantity of water, can promote new B acid site, surface to generate.Water/HY mass ratio is in 0-40%, and increasing the B acid site generates with the water yield increases, further increase the water addition after, the original acidic site in HY molecular sieve surface is capped, acid reduction.
The described Mo of containing catalyst is the bimetallic sulfide that Mo and transition metal are formed; Described transition metal is selected from least a among Ni, Fe and the Co, preferred Ni; The mass ratio of described Mo and described transition metal is 1: 0.5-2 was specially preferred 3: 22: 1,3: 2,1: 1,2: 3 or 1: 2;
Described solid acid supported V III family metal oxide catalyst is 1 with the mass ratio that contains the Mo catalyst: 0.1-1 was specially preferred 1: 0.3 1: 0.1,1: 0.3,1: 0.5,1: 0.7,1: 1 or 1: 1.6.
The method of the described carbon monoxide-olefin polymeric of preparation provided by the invention comprises the steps:
1) after VIII family metal oxide presoma is water-soluble, add described solid acid and carry out incipient impregnation, calcine after the standing and drying again, obtain described solid acid supported V III family metal oxide catalyst;
2) mixing in hydrogen atmosphere reacts with Mo-transition metal alloy oxides and Cosan, and reaction finishes and obtains the described Mo of containing catalyst; Wherein, described transition metal is selected from least a among Ni, Fe and the Co;
3) with described step 1) gained solid acid supported V III family metal oxide catalyst and described step 2) gained contains Mo catalyst mixing, obtains described carbon monoxide-olefin polymeric.
In the step 1) of said method, described VIII family metal oxide presoma is selected from least a in halide, nitrate and the sulfate of VIII family metallic element; Described VIII family metal oxide forerunner physical efficiency is water-soluble; Metallic element in the described VIII family metal oxide presoma is selected from least a among Ir, Pt, Ru, Pd and the Rh, preferred Rh;
In the water-soluble step of described VIII family metal oxide presoma, the mass ratio of described VIII family metal oxide presoma, water and described solid acid is 1: 0.5-100: 0.5-100, be specially preferred 1: 23.5: 19.2 (corresponding metal simple-substance load quality percentage on solid acid is 0.5%-5%) 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; The consumption of described water is the saturated water adsorptive value of described solid acid;
Described solid acid passes through vacuum drying treatment in advance; This vacuum drying method is conventional method, as long as with the moisture removal in the solid acid.
Described step 2) in, the mass ratio of described Mo-transition metal alloy oxides and Cosan is 1: 1-4 was specially preferred 1: 21: 1,1: 3 or 1: 4; In the described Mo-transition metal alloy oxides, the mass ratio of described Mo and transition metal is 1: 0.5-2 was specially preferred 3: 22: 1,3: 2,1: 1,2: 3 or 1: 2; In the described reactions steps, temperature is 250-360 ℃, and preferred 340 ℃, the time is 1-5 hour, preferred 4 hours;
The preparation method of described Mo-transition metal alloy oxides is sol-gal process, after specifically comprising the steps: the proportioning mixing of the aqueous solution according to Mo and transition metal with the nitrate aqueous solution of transition metal and ammonium molybdate, in 80 ℃ of waters bath with thermostatic control, heat, stir, dropwise add citric acid solution, and in 80 ℃ of constant temperature stirrings, impel the complex compound polymerization to generate gel, evaporate to dryness, obtain xerogel, place the Muffle furnace program to be warming up to 500 ℃, constant temperature 4 hours, be cooled to room temperature, obtain described Mo-transition metal alloy oxides powder.
In the described step 3), described solid acid supported V III family metal oxide catalyst is 1 with the mass ratio that contains the Mo catalyst: 0.1-1 was specially preferred 1: 0.3 1: 0.1,1: 0.3,1: 0.5,1: 0.7 or 1: 1.
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, polycyclic aromatic hydrocarbon, described carbon monoxide-olefin polymeric and water is mixed react, and reaction finishes and finishes described hydrogenation of polycyclic aromatic hydrocarbons open loop.
In the said method, described polycyclic aromatic hydrocarbon is selected from least a in naphthalene and the naphthane, preferred naphthalene.
The mass ratio of described polycyclic aromatic hydrocarbon, described carbon monoxide-olefin polymeric is 6: 4-15, preferred 6: 9.5.
In the described reactions steps, Hydrogen Vapor Pressure is 3-6MPa, and temperature is 250-360 ℃, and the time is 1-4 hour.When temperature is higher, help cracking reaction.But simultaneously, when temperature is higher, can accelerate cracking reaction, and then generate many little molecular product, and the condensation reaction of catalyst surface increases generation green coke presoma.For the acidity of controlling the side reaction that is caused by high temperature and regulating catalyst, add water to control reaction in the reaction, hydrone is in catalyst surface and reactant molecule competitive Adsorption, can suppress condensation reaction, and after hydrone covers on the part acidic site, can prevent that cracking reaction from further taking place.
Inquire into as follows to Related Mechanism of the present invention: through discovering, in naphthalene selective hydrogenation ring-opening reaction, the principal element that influences the open-loop products productive rate comprises the following aspects, the one, because course of reaction mainly comprises hydrogenation and the reaction of cracking two classes, if hydrogenation activity is strong excessively, then the corresponding meeting of cracking reaction is suppressed, on the other hand, if the bronsted acid of catalyst system is stronger, then lytic activity is strong excessively, can cross cracking and generate little molecule and high molecular weight product even coke.The 2nd, temperature is bigger to the influence of reaction, and according to thermodynamic study, lower temperature is conducive to hydrogenation reaction, and higher temperature is conducive to cracking.Under the lower condition of temperature, mainly generate hydrogenation products, under the temperature conditions of higher, it is serious to cross cracking.Therefore, selecting the suitable catalyst of a kind of hydrogenation and cracking activity coupling is the key that obtains high open-loop products productive rate.Among the present invention, with Mo-Ni catalyst and Rh
2O
3After/HY mixed, the productive rate of open-loop products obviously improved, and the Mo-Ni catalyst forms the bronsted acid site in hydrogen, improved the acidity of catalyst system.After adding suitable quantity of water, with the molecular sieve carrier effect, generate new bronsted acid site on the one hand, on the other hand, the inhibitory reaction thing generates high molecular weight product in the catalyst surface condensation reaction, and the productive rate of open-loop products further improves.
The present invention compared with prior art has the following advantages: 1, the present invention is at Rh
2O
3Mix the Mo-Ni catalyst among the/HY, improved the acidity of catalyst system.And reduced the cost of catalyst, and preparation is simple.2, make water as additive among the present invention, can significantly improve the productive rate of target product, environmental protection again, regulation and control easily.
Description of drawings
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 picture library.
The specific embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can get from open commercial sources if no special instructions.All available from west, Shantou Gansu Province chemical company (GuangZhou, China), Cosan, rhodium chloride and normal heptane are available from Beijing chemical reagents corporation for following described two kinds of used naphthalenes and naphthane, and it is pure that all medicines are analysis.The HY molecular sieve is bought from Taixing, Zibo chemical company (Chinese Shandong).
Embodiment one: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve was placed vacuum drying 10 hours, with 0.0051g RhCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good HY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12 hours, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ HY.
With 6.34g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=2/3) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take by weighing 5mg Rh
2O
3/ HY and Mo-Ni oxide 1.5mg, Cosan 3mg after the physical mixed, namely get carbon monoxide-olefin polymeric.
Embodiment two: the preparation of carbon monoxide-olefin polymeric
0.098g ZSM molecular sieve is placed vacuum drying 10h, with 0.0051g RhCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good ZSM molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ ZSM.
With 6.34g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=2/3) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take by weighing 5mg Rh
2O
3/ ZSM and Mo-Ni oxide 1.5mg, Cosan 3mg after the physical mixed, namely get carbon monoxide-olefin polymeric.
Embodiment three: the preparation of carbon monoxide-olefin polymeric
0.098g BETA molecular sieve is placed vacuum drying 10h, with 0.0051g RhCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good BETA molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ BETA.
With 6.34g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=2/3) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take by weighing 5mg Rh
2O
3/ BETA and Mo-Ni oxide 1.5mg, Cosan 3mg after the physical mixed, namely get carbon monoxide-olefin polymeric.
Embodiment four: the preparation of carbon monoxide-olefin polymeric
0.098g USY molecular sieve is placed vacuum drying 10h, with 0.0051g RhCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good USY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ USY.
With 6.34g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=2/3) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take by weighing 5mg Rh
2O
3/ USY and Mo-Ni oxide 1.5mg, Cosan 3mg after the 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 vacuum drying 10h, with 0.0051g RhCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good MCM-22 molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ MCM-22.
With 6.34g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=2/3) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take by weighing 5mg Rh
2O
3/ MCM-22 and Mo-Ni oxide 1.5mg, Cosan 3mg after the physical mixed, namely get carbon monoxide-olefin polymeric.
Embodiment six: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve is placed vacuum drying 10h, with 0.0037g IrCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good HY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Ir then
2O
3/ HY.
With 6.34g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=2/3) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take by weighing 5mg Ir
2O
3/ HY and Mo-Ni oxide 1.5mg, Cosan 3mg after the physical mixed, namely get carbon monoxide-olefin polymeric.
Embodiment seven: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve is placed vacuum drying 10h, with 0.0033g PdCl
2Be dissolved in the 0.12g distilled water, the dissolving back adds the good HY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets PdO/HY then.
With 6.34g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=2/3) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take by weighing 5mg PdO/HY and Mo-Ni oxide 1.5mg, Cosan 3mg, after the physical mixed, namely get carbon monoxide-olefin polymeric.
Embodiment eight: the preparation of carbon monoxide-olefin polymeric
0.099g HY molecular sieve is placed vacuum drying 10h, with 0.0013g RhCl
3H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good HY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ HY.
With 6.34g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=2/3) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take by weighing 5mg Rh
2O
3/ HY and Mo-Ni oxide 1.5mg, Cosan 3mg after the physical mixed, namely get carbon monoxide-olefin polymeric.
Embodiment nine: the preparation of carbon monoxide-olefin polymeric
0.095g HY molecular sieve is placed vacuum drying 10h, with 0.128g RhCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good HY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ HY.
With 6.34g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=2/3) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take by weighing 5mg Rh
2O
3/ HY and Mo-Ni oxide 1.5mg, Cosan 3mg after the physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment ten: the preparation of carbon monoxide-olefin polymeric
With 1.1g 0.9g Fe (NO
3)
39H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes then that (transition metal/Mo=2/3), stirs, dropwise adds the citric acid solution of finite concentration, volume at heating in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels complex compound polymerization generation gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-ferriferous oxide powder.
0.098g HY molecular sieve is placed vacuum drying 10h, with 0.0051g RhCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good HY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ HY.Get 1.5mg then, with 3mg Cosan, 5mg Rh
2O
3After/HY the physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 11: the preparation of carbon monoxide-olefin polymeric
With 1.1g Co (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes then that (transition metal/Mo=2/3), stirs, dropwise adds the citric acid solution of 1g/ml at heating in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels complex compound polymerization generation gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-cobalt/cobalt oxide powder.
0.098g HY molecular sieve is placed vacuum drying 10h, with 0.0051g RhCl
3H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good HY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ HY.Get 1.5mg then, with 3mg Cosan, 5mg Rh
2O
3After/HY the physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 12: the preparation of carbon monoxide-olefin polymeric
With 4.78g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=1/2) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.
0.098g HY molecular sieve is placed vacuum drying 10h, with 0.0051g RhCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good HY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ HY.Get 1.5mg then, with 3mg Cosan, 5mg Rh
2O
3After/HY the physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 13: the preparation of carbon monoxide-olefin polymeric
With 19.13g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes then that (transition metal/Mo=2/1), stirs, dropwise adds the citric acid solution of 1g/ml at heating in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels complex compound polymerization generation gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-cobalt/cobalt oxide powder.
0.098g HY molecular sieve is placed vacuum drying 10h, with 0.0051g RhCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good HY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ HY.Get 1.5mg molybdenum-cobalt/cobalt oxide powder then, with 3mg Cosan, 5mg Rh
2O
3After/HY the physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 14: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve is placed vacuum drying 10h, with 0.0051g RhCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good HY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ HY.
With 6.34g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=2/3) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take by weighing 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 the physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 15: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve is placed vacuum drying 10h, with 0.0051g RhCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good HY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ HY.
With 6.34g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=2/3) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take by weighing 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 the physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 16: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve is placed vacuum drying 10h, with 0.0051g RhCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good HY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ HY.
With 6.34g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=2/3) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take by weighing 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 the physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 17: the preparation of carbon monoxide-olefin polymeric
0.098g HY molecular sieve is placed vacuum drying 10h, with 0.0051g RhCl
33H
2O is dissolved in the 0.12g distilled water, and the dissolving back adds the good HY molecular sieve of vacuum drying fully, behind the incipient impregnation, leaves standstill 12h, places Muffle furnace to calcine after 100 ℃ of dryings, and calcination condition is: 5 ℃/min is warming up to 550 ℃, and constant temperature 3h namely gets Rh then
2O
3/ HY.
With 6.34g Ni (NO
3)
26H
2O is dissolved in wiring solution-forming in the 5ml water, with 1g (NH
4)
6Mo
7O
244H
2O is dissolved in wiring solution-forming in the 5ml water, mixes (transition metal/Mo mol ratio=2/3) then, heats, stirs, dropwise adds the citric acid solution of 1g/ml in 80 ℃ of waters bath with thermostatic control, and solution stirs in 80 ℃ of constant temperature, impels the complex compound polymerization to generate gel.Evaporate to dryness obtains xerogel then.Be placed on that program is warming up to 500 ℃ in the Muffle furnace, constant temperature 4 hours is cooled to room temperature, obtains ultra-fine molybdenum-nickel oxide powder.Take by weighing 5mg Rh
2O
3/ HY and Mo-Ni oxide 1.5mg, Cosan 6mg, i.e. Mo-Ni oxide: Cosan (mass ratio)=1: 4.After the physical mixed, obtain carbon monoxide-olefin polymeric.
Embodiment 18:
With the 6mg naphthalene, the catalyst 9.5mg that embodiment one is prepared, 2mg water adds in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, put into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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: the chromatographic column model: DB-5ms 30m0.25mm, the column temperature condition is: 50 ℃ kept 2 minutes, were warming up to 250 ℃ with 10 ℃/min, kept 30 minutes, split ratio: 10: 1, injector temperature: 250 ℃; The mass spectrum condition is: ion source temperature: 200 ℃, electron energy 70eV, sweep limits: 20-650m/z, gained the results are shown in Figure 1 and table 1.
Table 1 gas chromatography mass spectrometry goes out the peak report
By with the comparison of NIST standard picture library, the most probable structure of each peak correspondence in the analysis diagram 1, as shown in Figure 2.By Fig. 1 and Fig. 2 as can be known, be numbered the equal corresponding open-loop products in peak of 1-29,31-33, be mainly alkyl naphthene and alkyl cyclohexene compounds, be numbered 30 the corresponding hydrogenation products trans-decalin in peak, be numbered the corresponding hydrogenation products cis-decaline in peak, 34 place, be numbered 35 the corresponding high molecular weight product in peak, be mainly Fluhyzon.Calculating the open-loop products productive rate is 63.1%.
Embodiment 19:
6mg naphthalene, embodiment two prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 22.5%.
Embodiment 20:
6mg naphthalene, embodiment three prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 31.7%.
Embodiment 21:
6mg naphthalene, embodiment four prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 42.2%.
Embodiment 22:
6mg naphthalene, embodiment five prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 37.9%.
Embodiment 23:
6mg naphthalene, embodiment six prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 60.9%.
Embodiment 24:
6mg naphthalene, embodiment seven prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 40.4%.
Embodiment 25:
6mg naphthalene, embodiment eight prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 45.6%.
Embodiment 26:
6mg naphthalene, embodiment nine prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 36.8%.
Embodiment 27:
6mg naphthalene, embodiment ten prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 56.3%.
Embodiment 28:
6mg naphthalene, embodiment 11 prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 50.7%.
Embodiment 29:
6mg naphthalene, embodiment 12 prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 56.9%.
Embodiment 30:
6mg naphthalene, embodiment 13 prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 51.4%.
Embodiment 31:
6mg naphthalene, embodiment 14 prepared catalyst 7.7mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 51.5%.
Embodiment 32:
6mg naphthalene, embodiment 15 prepared catalyst 14.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 41.3%.
Embodiment 33:
6mg naphthalene, embodiment 16 prepared catalyst 8mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 53.6%.
Embodiment 34:
6mg naphthalene, embodiment 17 prepared catalyst 12.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 32.3%.
Embodiment 35:
6mg naphthalene, embodiment one prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 1h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 2.9%.
Embodiment 36:
6mg naphthalene, embodiment one prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 2h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 7.98%.
Embodiment 37:
6mg naphthalene, embodiment one prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 3h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 29.49%.
Embodiment 38:
6mg naphthalene, embodiment one prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 5h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 47.44%.
Embodiment 39:
6mg naphthane, embodiment one prepared catalyst 9.5mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 72.34%.
Embodiment 40:
6mg naphthalene, embodiment one prepared catalyst 15mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, puts into reactor after the temperature constant, pick up counting, behind the reaction 5h, use the 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 do not have substantive difference, and only the peak area of each product is slightly different.Calculating the open-loop products productive rate is 42.64%.
Embodiment 41:
6mg naphthalene, embodiment one prepared catalyst 4mg, 2mg water are added in the autoclave, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, put into reactor after the temperature constant, pick up counting, behind the reaction 5h, use the washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, calculating the open-loop products productive rate is 47.44%.
Embodiment 42:
With 6mg naphthalene, 9mg Rh
2O
3/ HY, 2mg water add in the reactor, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, put into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 the reactor, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, put into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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:
With 6mg naphthalene, 6mg Rh
2O
3/ HY, 3mg Cosan, 2mg water add in the reactor, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, put into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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 the reactor, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, put into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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:
With 6mg naphthalene, 4.5mg Mo-Ni, 5mg Rh
2O
3/ HY, 2mg water add in the reactor, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, put into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the 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:
With 6mg naphthalene, 1.5mg Mo-Ni, 3mg Cosan, 5mg Rh
2O
3/ HY, 2mg water add in the reactor, the sealing back feeds 5MPa hydrogen, simultaneously the reacting furnace temperature is controlled at 340 ℃, put into reactor after the temperature constant, pick up counting, behind the reaction 4h, use the washed with heptane reactor, take out product, add biphenyl as interior mark, adopt gas chromatographic analysis, gained the results are shown in Table 2.
Table 2, different catalysts component are to the influence of naphthalene selective hydrogenation ring-opening reaction
In the table 2, open-loop products is mainly alkyl cyclohexane and alkyl cyclohexene, and high molecular weight product is mainly Fluhyzon, hydrogenation products is mainly trans-decahydronaphthalene and cis-decahydronaphthalene.
Embodiment 42-47 has illustrated the effect of combination catalyst different component catalysis naphthalene selective hydrogenation ring-opening reaction, and when Rh catalyst and Mo-Ni catalyst used separately, the open-loop products productive rate was not high, as Rh
2O
3/ HY catalytic reaction gained open-loop products has only 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 were used, the open-loop products productive rate obviously increased, and continued to increase after adding sulphur.
Embodiment 48:
With 6mg naphthalene, 5mg Rh
2O
3/ HY, 1.5mg Mo-Ni, 3mg Cosan add in the reactor, feed 5MPa hydrogen, and temperature is controlled at 340 ℃, behind the reaction 4h, use the washed with heptane reactor, add biphenyl as interior mark, adopt gas chromatographic analysis, and gained the results are shown in Table 3.
Embodiment 49:
With 6mg naphthalene, 5mg Rh
2O
3/ HY, 1.5mg Mo-Ni, 3mg Cosan, 6mg water add in the reactor, feed 5MPa hydrogen, and temperature is controlled at 340 ℃, behind the reaction 4h, use the washed with heptane reactor, add biphenyl as interior mark, adopt gas chromatographic analysis, and gained the results are shown in Table 3.
Embodiment 50:
With 6mg naphthalene, 5mg Rh
2O
3/ HY, 1.5mg Mo-Ni, 3mg Cosan, 10mg water add in the reactor, feed 5MPa hydrogen, and temperature is controlled at 340 ℃, behind the reaction 4h, use the washed with heptane reactor, add biphenyl as interior mark, adopt gas chromatographic analysis, and gained the results are shown in Table 3.
Embodiment 51:
With 6mg naphthalene, 5mg Rh
2O
3/ HY, 1.5mg Mo-Ni, 3mg Cosan, 50mg water add in the reactor, feed 5MPa hydrogen, and temperature is controlled at 340 ℃, behind the reaction 4h, use the washed with heptane reactor, add biphenyl as interior mark, adopt gas chromatographic analysis, and gained the results are shown in Table 3.
Embodiment 52:
With 6mg naphthalene, 5mg Rh
2O
3/ HY, 1.5mg Mo-Ni, 3mg Cosan, 100mg water add in the reactor, feed 5MPa hydrogen, and temperature is controlled at 340 ℃, behind the reaction 4h, use the washed with heptane reactor, add biphenyl as interior mark, adopt gas chromatographic analysis, and gained the results are shown in Table 3.
Embodiment 53:
With 6mg naphthalene, 5mg Rh
2O
3/ HY, 1.5mg Mo-Ni, 3mg Cosan, 400mg water add in the reactor, feed 5MPa hydrogen, and temperature is controlled at 340 ℃, behind the reaction 4h, use the washed with heptane reactor, add biphenyl as interior mark, adopt gas chromatographic analysis, and gained the results are shown in Table 3.
Table 3, the water yield are to the influence of naphthalene selective hydrogenation ring-opening reaction
In the table 3, open-loop products is mainly alkyl cyclohexane and alkyl cyclohexene, and high molecular weight product is mainly Fluhyzon, hydrogenation products is mainly trans-decahydronaphthalene and cis-decahydronaphthalene.
Embodiment 48-53 is the influences of different water additions to reacting, and reaction has facilitation to low amounts of water for selective opening, and with the increase of rate of water added, ring-opening reaction is suppressed earlier, and hydrogenation sites is also capped then, and hydrogenation reaction is suppressed.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210063611.1A CN103301874B (en) | 2012-03-12 | 2012-03-12 | Method for improving selective hydrogenation ring opening of polycyclic aromatic hydrocarbon and catalyst composition thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210063611.1A CN103301874B (en) | 2012-03-12 | 2012-03-12 | Method for improving selective hydrogenation ring opening of polycyclic aromatic hydrocarbon and catalyst composition thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103301874A true CN103301874A (en) | 2013-09-18 |
| CN103301874B CN103301874B (en) | 2015-03-11 |
Family
ID=49127849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210063611.1A Expired - Fee Related CN103301874B (en) | 2012-03-12 | 2012-03-12 | Method for improving selective hydrogenation ring opening of polycyclic aromatic hydrocarbon and catalyst composition thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103301874B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109395726A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Fused ring compound selective hydrocatalyst |
| CN112570005A (en) * | 2019-09-30 | 2021-03-30 | 中国石油化工股份有限公司 | Method for regulating and controlling metal hydrogenation activity in reaction system and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769385A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | A kind of middle distillate oil hydrogenation treatment catalyst and preparation method thereof |
| US20110319684A1 (en) * | 2008-12-18 | 2011-12-29 | Siqin Li | Method for selective hydrogenation of phenylacetylene using composite bed in the presence of styrene |
-
2012
- 2012-03-12 CN CN201210063611.1A patent/CN103301874B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769385A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | A kind of middle distillate oil hydrogenation treatment catalyst and preparation method thereof |
| US20110319684A1 (en) * | 2008-12-18 | 2011-12-29 | Siqin Li | Method for selective hydrogenation of phenylacetylene using composite bed in the presence of styrene |
Non-Patent Citations (2)
| Title |
|---|
| S.M.A.M.BOUWENS,ET AL.: "The Role of Ni in Sulfided Carbon-Supported Ni-Mo HydrodesuIfurization Catalysts", 《JOURNAL OF CATALYSIS》, vol. 131, 31 December 1991 (1991-12-31) * |
| 柴永明等: "过渡金属硫化物催化剂催化加氢作用机理", 《化学进展》, vol. 19, no. 23, 31 March 2007 (2007-03-31) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109395726A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Fused ring compound selective hydrocatalyst |
| CN109395726B (en) * | 2017-08-18 | 2021-09-03 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of fused ring compounds |
| CN112570005A (en) * | 2019-09-30 | 2021-03-30 | 中国石油化工股份有限公司 | Method for regulating and controlling metal hydrogenation activity in reaction system and application thereof |
| CN112570005B (en) * | 2019-09-30 | 2023-08-04 | 中国石油化工股份有限公司 | Method for regulating and controlling metal hydrogenation activity in reaction system and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103301874B (en) | 2015-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101550051B (en) | Process for preparing arene selectivity by enhancing methanol aromatizatian and process for preparation of catalyst thereof | |
| CN109550501B (en) | Preparation method and application of nitrobenzene liquid-phase hydrogenation aniline preparation catalyst | |
| CN112191254B (en) | Catalyst and method for preparing 2-ethoxyphenol by catalytic depolymerization of lignin | |
| CN104399520B (en) | Catalyst for producing high-octane-number gasoline composition from heavy aromatic hydrocarbons and preparation method of catalyst | |
| Yu et al. | Hydrocracking of naphthalene over Beta zeolite coupled with NiMo/γ-Al2O3: Investigation of metal and acid balance based on the composition of industrial hydrocracking catalyst | |
| CN107626343A (en) | A kind of one-step method from syngas prepares catalyst of light aromatics and preparation method and application | |
| CN106824259A (en) | For the method for preparation and use of the catalyst of ethanol conversion 1,3 butadiene of system | |
| WO2015032189A1 (en) | Catalyst used for resource utilization of a fixed bed aniline distillation residue and method for preparing said catalyst | |
| CN107970949A (en) | A kind of three selective hydrogenation catalyst of carbon, preparation method and method of hydrotreating | |
| CN101121632A (en) | The preparation method of hanging tetrahydrodicyclopentadiene | |
| CN103301874A (en) | Method for improving selective hydrogenation ring opening of polycyclic aromatic hydrocarbon and catalyst composition thereof | |
| CN115504892B (en) | Method for synthesizing procaine by continuous catalytic hydrogenation | |
| CN103418405B (en) | Replenishment catalyst for maintaining stabilization production of acrylonitrile device | |
| CN104549318A (en) | Catalyst for preparing furfuryl alcohol through hydrogenating furfural liquid phase and preparation method of catalyst | |
| CN110227536A (en) | It is a kind of for the NiMoW/MCM-41 composite catalyst of sad hydrogenation deoxidation and its preparation and application | |
| CN107970954B (en) | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and preparation method thereof | |
| CN109174159A (en) | A kind of novel fixed point adds deuterium photochemical catalyst | |
| CN105582920A (en) | Dehydrogenation catalyst for light alkanes and application of dehydrogenation catalyst | |
| CN1613557A (en) | Carrier superfine alloy hydrogenation catalyst for dearomatization and its preparation | |
| CN108043452B (en) | Propane and methanol mixed aromatization catalyst, preparation method and application | |
| CN102626652B (en) | Molecular sieve catalyst for purifying methane in tail gas of natural gas vehicles, preparation and application thereof | |
| CN106423202A (en) | Preparation method of rhodium-ruthenium composite catalyst for preparing ethyl alcohol through acetic acid hydrogenation | |
| CN105562007B (en) | A kind of ferrous metals oxide catalyst and its preparation method and application | |
| CN105727977A (en) | Preparation method of catalyst for synthetic gas methanation to substitute natural gas | |
| CN108178732B (en) | A kind of preparation method of N-methyl p-methoxyaniline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150311 |