CN101767032A - Deep hydrodesulfurization solid-acid catalyst of gasoline and preparation method thereof - Google Patents
Deep hydrodesulfurization solid-acid catalyst of gasoline and preparation method thereof Download PDFInfo
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- 239000003502 gasoline Substances 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011973 solid acid Substances 0.000 title claims abstract description 17
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 229910021536 Zeolite Inorganic materials 0.000 claims description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 19
- 239000010457 zeolite Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002161 passivation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 23
- 239000005864 Sulphur Substances 0.000 abstract description 6
- 238000005899 aromatization reaction Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002808 molecular sieve Substances 0.000 abstract description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 238000004227 thermal cracking Methods 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 description 19
- 229910052717 sulfur Inorganic materials 0.000 description 17
- 239000011593 sulfur Substances 0.000 description 17
- 230000009257 reactivity Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006477 desulfuration reaction Methods 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 5
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 3
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 3
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 101150019148 Slc7a3 gene Proteins 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the chemical field, in particular to a deep hydrodesulfurization solid-acid catalyst of gasoline and a preparation method thereof. Keggin-structure polyoxometallate (POM) is carried on a nano-sized ZSM-5 molecular sieve, and nickel nitrate is added to improve the catalytic performance of the catalyst. The invention is applicable to the modification of gasolines such as FCC gasoline, DCC gasoline, thermal cracking gasoline, coker gasoline and the like. The sulphur content in the gasoline treated by the catalyst is greatly reduced, and the catalyst has good low-temperature aromatization performance and is an ideal desulfurating, olefin-reducing and low-temperature aromatization catalyst.
Description
Technical field
The present invention relates to chemical field, be specifically related to a kind of deep hydrodesulfurizationsolid solid-acid catalyst of gasoline and preparation method thereof.
Background technology
The content of China finished product FCC gasoline olefin is up to 40-55%, and sulfur content is 200-1500 μ g/g, and the two is the principal element that motor vehicle exhaust emission causes environmental pollution.The stability that the content that reduces sulfur in gasoline and alkene can strengthen gasoline helps the use of engine, also reduces the discharge capacity of volatile organism in the vehicle exhaust, NOx and SOx simultaneously.Therefore, in the clean gasoline standard alkene and sulfur content have all been done strict qualification.China's gasoline product will reach state IV discharging gradually and promptly approach Europe IV standard, requires sulfur in gasoline content ≯ 50 μ g/g, olefin(e) centent ≯ 20vol.%, arene content ≯ 35vol.%, in future, international and domestic sulfur in gasoline content reaches ≯ 10 μ g/g, even does not have the sulphur requirement.Therefore, the manufacture a finished product petroleum chemical enterprise of gasoline of China will be faced with stern challenge.
The hydro-upgrading technology not only can remove the sulphur of mercaptan in the gasoline fraction and other higher boiling ranges, can also control olefin content in gasoline and sulfur content effectively under the prerequisite that does not reduce octane number, is subjected to the extensive concern of each major oil companies and research institution.Exploitation can reduce alkene and sulfur content in the FCC gasoline significantly, keeps less loss of octane number simultaneously and even increases and the technology of high liquid yield is the emphasis of current Technology for Producing Clean Gasoline.
The research of deep hydrodesulfurizationof is usually to screen than Co-Mo, Ni-Mo and higher active component and the exploitation specific activity Al of NiW
2O
3More excellent carrier is main.At present, remove Al
2O
3Also comprise active C outward, y-type zeolite, TiO
2And mesoporous zeolite (as SBA-15 and MCM-41) etc.Chunshan Song and Kondam Madhusudan Reddy have reported the article that is entitled as " Mesoporous molecular sieve MCM-41 supported Co-Mocatalyst for hydrodesulfurization of dibenzothiophene in distillate fuels " on periodical AppliedCatalysis A:General.Their result of study shows, with the catalyst of the NiMo of MCM-41 load and CoMo to the activity of dibenzo thiophene phenol be higher than with the conventional method preparation with Al
2O
3Be the catalyst of carrier, but it is active in industrial deep hydrodesulfurizationof catalyst.
U.S. Pat P4,140,626 disclose a kind of with Al
2O
3With MgO be the catalyst of carrier, wherein contain CoO (3wt%), MoO
3(16wt%), MgO (70wt%) and Al
2O
3Its desulfurization degree of catalyst (11wt%) reaches 94%, and the alkene saturation factor is 64%.Cause bad mechanical strength to be difficult to satisfy the commercial Application needs owing to containing a large amount of MgO in this catalyst.
U.S. Pat P 5,340,466 to have introduced a kind of aluminium oxide and hydrotalcite of adopting be the catalyst for selectively hydrodesulfurizing of carrier, this catalyst is under desulfurization degree is situation more than 90%, the alkene saturation factor is 30-40%, demonstrate good desulfuration selectivity, but the less stable of this catalyst.
U.S. Pat P 6,042, and 719 disclose a kind of FCC catalyst for selective hydrodesulfurizationof of gasoline, and this catalyst is with ZSM-5 and Co-Mo/Al
2O
3The catalyst of forming complex carrier.After cutting (below 90 ℃) the gasoline component processing for 490 μ g/g, sulfur content can be reduced to 100 μ g/g, 2.5 units of the uprising index loss of product.For sulfur content is the heavy oil component of 14200 μ g/g, and the product sulfur content is less than 40 μ g/g, and the uprising index of product increases by 0.7 unit.This catalyst stability is relatively poor, is difficult to satisfy long-term industrial operation needs.
Lilia Lizama and Tatiana Klimova have delivered on periodical Applied Catalysis B:Environmental 82 (2008) 138-15 and have been entitled as " Klimova Highly active deep HDS catalysts prepared using Mo and Wheteropolyacids supported on SBA-15 " article.The author has reported that in article adopting mesoporous SBA-15 is carrier loaded phosphorus tungsten and phosphorus molybdenum POM, is that the result of study of probe molecule shows that this catalyst has reached the active effect of deep hydrodesulfurizationof with the hydrodesulfurization of 4 ' 6-dimethyl dibenzo thiophene phenol.
Duan Aijun and Huang Weiqiang etc. have reported that at Chinese patent CN101199935 a kind of synthetic reaching with these composite oxides of aluminum titanium composite oxide material is carrier load type deep hydrodesulfurizationof catalyst, in the reaction of diesel oil hydrogenation deep desulfuration, can reach desulfurization degree 99%, operation carries out under the condition that relaxes, can be removed to sulfide in diesel oil below the 15 μ g/g from 1300 μ g/g, or be removed to below the 1 μ g/g from 430 μ g/g, sulfur content can satisfy Europe IV standard in the product.
U.S. Pat P 5,865, and 988 have introduced a kind of low-quality gasoline upgrading technology of Mobil company exploitation.This process using two step method is carried out upgrading to gasoline, at first with raw gasoline by containing Co-Mo/Al
2O
3The bed of catalyst, hydrogenation and removing sulfide makes part alkene saturated simultaneously; Then with the product that generates previously by containing the bed of ZSM-5 catalyst, to recover the saturated loss of octane number that causes of alkene in hydrogenation process.This technology can reduce sulfur content and the olefin(e) centent in the gasoline significantly, increases arene content.
A kind of low-quality gasoline upgrading technology has also been introduced at USP 5,041 by Mobil company in 028 patent, the USY that this process using supports Pt, Re, Ir etc. is a catalyst, and arene content obviously increases when reducing alkene and sulfur content significantly.
Introduced a kind of catalytic gasoline upgrading system clean gasoline Preparation of catalysts method that is used among the CN1594506A, this method proposes to be prepared by nano-ZSM-5 molecular sieve, inorganic oxide, based metallic oxides with mixed rare earth and zinc, gallium oxide the new method of catalyst, this catalyst is used for the content that the catalytic gasoline upgrading can reduce alkene, sulphur and benzene, and octane number remains unchanged or slightly improves.
Zhao Xiaobo and Guo Xinwen etc. [petroleum journal (PETROLEUM PROCESSING) 2006,22 (6): 20-23] have reported the article that is entitled as the application of modified Nano HZSM-5 catalyst in the FCC gasoline upgrading.They studies show that, the nanometer HZSM-5 catalyst of hydrothermal treatment consists and oxide-metal combinations modification has desirable desulphurizing ability, and under 370 ℃ of conditions of reaction temperature, the sulphur mass fraction is reduced to 39.1 μ g/g by 181.2 μ g/g.
Summary of the invention
The purpose of this invention is to provide a kind of highly active FCC gasoline deep hydrodesulphurization catalyst, after this catalyst treatment, can reduce the sulfur content in the gasoline significantly, have good olefine selective and increase aromatic production, this catalyst increases the content of high-octane rating isomers by the skeletal isomerization of alkene and alkane simultaneously.
Technical scheme of the present invention is: a kind of deep hydrodesulfurizationsolid solid-acid catalyst of gasoline is a raw material with nickel nitrate, nanometer HZSM-5 zeolite, boehmite (aluminium oxide) and polyoxometallate (POM), and the quality percentage composition of each raw material is as follows:
Nickel nitrate: 0.4～8%
Nanometer HZSM-5 zeolite: 52～80%
Boehmite (aluminium oxide): 15～20%
POM： 4～20％
The preparation method of above-mentioned a kind of deep hydrodesulfurizationsolid solid-acid catalyst of gasoline, step is as follows:
(1) the nanometer NaZSM-5 of preparation 100nm:
Under normal temperature, normal pressure, the nano-ZSM-5 zeolite sample mixes by 4: 1 mass ratioes with carrier boehmite (aluminium oxide) after burning amine, with the HNO of 10wt%
3Solution bonding and extruded moulding, drying, temperature-programmed calcination makes the nanometer NaZSM-5 of 100nm;
(2) preparation nanometer HZSM-5 zeolite:
With the nanometer NaZSM-5 of the 100nm of step (1) preparation, with the NH of concentration 0.4mol/L
4NO
3Solution normal temperature exchange secondary makes nanometer HZSM-5 zeolite after drying, roasting and 500 ℃ of aqueous vapor passivation again;
(3) preparation NiHZSM-5:
Get nickel nitrate and nanometer HZSM-5 zeolite by the quality percentage composition of above-mentioned raw materials, then nickel nitrate is dissolved in preparation quality concentration in the deionized water and is 10～25% solution, stir and obtain blue settled solution after 5～10 minutes, adopt equi-volume impregnating to be impregnated on the nanometer HZSM-5 of aqueous vapor passivation zeolite, through 100～150 ℃ of oven dry 10～15h, 350～540 ℃ of roasting 3～5h obtain NiHZSM-5, and optimum calcination temperature is 300～400 ℃;
(4) prepare solid acid catalyst:
Quality percentage composition by above-mentioned raw materials is got POM, then POM is dissolved in preparation quality concentration in the deionized water and is 10～25% solution, adopt equi-volume impregnating to be impregnated on the NiHZSM-5 then, through 100～150 ℃ of oven dry 10～15h, 350～540 ℃ of roasting 3～5h, make solid acid catalyst, optimum calcination temperature is 300～400 ℃.
Be applied to the gasoline upgrading desulphurization reaction, suitable reaction temperature is 240～300 ℃.
The present invention supports Keggin structure polyoxometallate (POM) on nanoscale ZSM-5 molecular sieve, and introduces the catalytic performance that nickel nitrate improves catalyst.The present invention is applicable to the upgrading of gasoline such as catalytic cracking (FCC) gasoline, catalytic pyrolysis (DCC) gasoline, pyrolysis gasoline, coker gasoline.
Effect of the present invention is: the upgrading that is applicable to gasoline such as catalytic cracking (FCC) gasoline, catalytic pyrolysis (DCC) gasoline, pyrolysis gasoline, coker gasoline.Through with the gasoline after this catalyst treatment, can reduce sulfur in gasoline content significantly, have good low-temperature aromatisation performance simultaneously, be a kind of more satisfactory desulfurization, fall alkene and low temperature aromatized catalyst.
Specific embodiment
FCC gasoline desulfur reaction: hydrogen flowing quantity is with mass flowmenter control and metering, and reaction raw materials FCC gasoline is squeezed into constant-flux pump, and enters beds after hydrogen mixes and reacts.Product is after gas-liquid separation, and liquid is discharged from the knockout drum bottom.Loaded catalyst 2g faces hydrogen activation 1h with 350 ℃ earlier, in 280 ℃ of reaction temperatures; H
2/ hydrocarbon is than 300; Air speed (WHSV): 0.8h
-1Condition react.The raw material that is adopted is the full cut FCC gasoline of Dalian Petrochemical Industry Company of CNPC: alkene 36.6vol.%; Aromatic hydrocarbons 17.8vol.%; Alkane 45.6vol.%, sulfur content 242 μ g/g; Research octane number (RON) 86.9.
The evaluation index that reaction result adopts is: olefin(e) centent (vol.%) :≤20%
Arene content (vol.%) :≤35%
Sulfur content (μ g/g) :≤30%
Comparative Examples 1
0.99g nickel nitrate is dissolved in the 4.5mL ionized water, agitation as appropriate obtains blue settled solution.Adopt equi-volume impregnating to be impregnated into the HZSM-5 zeolite of 10g aqueous vapor passivation, dry 12h, 350 ℃ of roasting 4h for 150 ℃.Obtain NiHZSM-5.
Comparative Examples 2
Take by weighing 1.0g phosphorus tungsten POM and be dissolved in the 4.5mL ionized water, stir and obtain colorless cleared solution.Adopt equi-volume impregnating to be impregnated on the NiHZSM-5 that makes according to Comparative Examples 1, behind the dipping 12h, in 150 ℃ of oven dry 12h, 540 ℃ of roasting 4h.Obtain Ni-P-W-HZSM-5.
Comparative Examples 3
Take by weighing the 0.67g lanthanum nitrate and be dissolved in the 4.5mL ionized water, stir and obtain colourless solution.Adopt equi-volume impregnating that it is impregnated on the HZSM-5 zeolite of 10g aqueous vapor passivation, in 150 ℃ of oven dry 12h, 350 ℃ of roasting 4h.Obtain LaHZSM-5.
0.99g nickel nitrate is dissolved in the 4.5mL ionized water, stirs to obtain blue settled solution.Adopt equi-volume impregnating that it is impregnated into above-mentioned 10.5g HZSM-5 zeolite, in 150 ℃ of oven dry 12h, 350 ℃ of roasting 4h.Obtain La-NiHZSM-5.
Take by weighing 1.0g phosphorus tungsten POM and be dissolved in the 4.5ml water, agitation as appropriate obtains colorless cleared solution.Adopt equi-volume impregnating that it is impregnated on the La-NiHZSM-5, behind the dipping 12h, in 150 ℃ of oven dry 12h, 350 ℃ of roasting 4h.Obtain the La-NiPW-HZSM-5 catalyst.
Comparative Examples 4
0.99g nickel nitrate is dissolved in the 4.5ml ionized water, agitation as appropriate obtains blue settled solution.Adopt equi-volume impregnating to be impregnated into the Al of 10g extruded moulding
2O
3On, 150 ℃ of oven dry 12h, 350 ℃ of roasting 4h obtain Ni-γ-Al
2O
3Catalyst.
Take by weighing 1.0g phosphorus tungsten POM and be dissolved in the 4.5ml water, agitation as appropriate obtains colorless cleared solution.Adopt equi-volume impregnating that it is impregnated into Ni-γ-Al
2O
3On, dipping 12h is in 150 ℃ of oven dry 12h, 350 ℃ of roasting 4h.Obtain Ni-PW-γ-Al
2O
3
Embodiment 1
Take by weighing 1.0g phosphorus tungsten POM and be dissolved in the 4.5ml water, agitation as appropriate obtains colorless cleared solution.Adopt equi-volume impregnating to be impregnated on the NiHZSM-5 that makes according to Comparative Examples 1, dipping 12h is in 150 ℃ of oven dry 12h, 350 ℃ of roasting 4h.Obtain Cat1.
Embodiment 2
Take by weighing 1.0g silicon tungsten POM and be dissolved in the 4.5ml water, agitation as appropriate obtains colorless cleared solution.Adopt equi-volume impregnating to be impregnated on the NiHZSM-5 that makes according to Comparative Examples 1, dipping 12h is in 150 ℃ of oven dry 12h, 350 ℃ of roasting 4h.Obtain Cat2.
Embodiment 3
Take by weighing 1.0g phosphorus molybdenum POM and be dissolved in the 4.5ml water, agitation as appropriate obtains yellow settled solution.Adopt equi-volume impregnating that it is impregnated on the NiHZSM-5 that makes according to Comparative Examples 1.Behind the dipping 12h, in 150 ℃ of oven dry 12h, 350 ℃ of roasting 4h.Obtain Cat3.
Embodiment 4
On fixed bed continuous reactor, estimate the reactivity worth of the solid acid catalyst Cat1 of embodiment 1 preparation:
Concrete reaction condition is as follows: reaction pressure is 2.0MPa, 280 ℃ of reaction temperatures, and the gasoline flow is 0.04ml/min, FCC gasoline air speed 0.8h
-1, H
2Flow 12ml/min.The reactivity worth data see Table 1.
Table 1 Cat1 catalyst reaction data result
Embodiment 5
On fixed bed continuous reactor, estimate the solid acid catalyst Cat2 reactivity worth of embodiment 2 preparations:
Concrete reaction condition is as follows: reaction pressure is 2.0MPa, 280 ℃ of reaction temperatures, and FCC gasoline flow is 0.04ml/min, FCC gasoline air speed 0.8h
-1, H
2Flow 12ml/min.The reactivity worth data see Table 2.
Table 2 Cat2 catalyst reaction data result
Embodiment 6
On fixed bed continuous reactor, estimate the reactivity worth of the composite solid-acid catalyst Cat3 of embodiment 3 preparations:
Concrete reaction condition is as follows: reaction pressure is 2.0MPa, 280 ℃ of reaction temperatures, and FCC gasoline flow is 0.04ml/min, FCC gasoline air speed 0.8h
-1, H
2Flow 12ml/min.The reactivity worth data see Table 3.
Table 3 Cat3 catalyst reaction data result
Embodiment 7
On fixed bed continuous reactor, estimate the reactivity worth of the NiHZSM-5 catalyst of Comparative Examples 1 preparation:
Concrete reaction condition is as follows: reaction pressure is 2.0MPa, 280 ℃ of reaction temperatures, and the gasoline flow is 0.04ml/min, FCC gasoline air speed 0.8h
-1, H
2Flow 12ml/min.The reactivity worth data see Table 4.
Table 4 NiHZSM-5 catalyst reaction data result
Embodiment 8
On fixed bed continuous reactor, estimate the reactivity worth of the Ni-P-W-HZSM-5 catalyst of Comparative Examples 2 preparations:
Concrete reaction condition is as follows: reaction pressure is 2.0MPa, 280 ℃ of reaction temperatures, and FCC gasoline flow is 0.04ml/min, FCC gasoline air speed 0.8h
-1, N
2Flow 12ml/min.The reactivity worth correction data sees Table 5.
Table 5 Ni-P-W-HZSM-5 catalyst result
Embodiment 9
On fixed bed continuous reactor, estimate the reactivity worth of the La-NiPW-HZSM-5 catalyst of Comparative Examples 3 preparations:
Concrete reaction condition is as follows: reaction pressure is 2.0MPa, 280 ℃ of reaction temperatures, and FCC gasoline flow is 0.04ml/min, FCC gasoline air speed 0.8h
-1, H
2Flow 12ml/min.The reactivity worth data see Table 6.
Table 6 La-NiPW-HZSM-5 catalyst reaction performance data result
Embodiment 10
On fixed bed continuous reactor, estimate the NiPW-γ-Al of Comparative Examples 4 preparations
2O
3The reactivity worth of catalyst:
Concrete reaction condition is as follows: reaction pressure is 2.0MPa, 280 ℃ of reaction temperatures, and FCC gasoline flow is 0.04ml/min, FCC gasoline air speed 0.8h
-1, H
2Flow 12ml/min.The reactivity worth data see Table 7.
Table 7 NiPW-γ-Al
2O
3The catalyst reaction performance data
From above-mentioned result of study as can be seen, (embodiment 4 under given condition in the catalyst of 350 ℃ of roastings in embodiment 1 and 3, embodiment 6) have a good deep desulfuration, the low temperature aromatisation, alkene and isomerization activity fall, in FCC gasoline hydrogenation modifying desulphurization reaction, when reaction temperature is 280 ℃, when feed sulphur content is 242ppm, desulfurization degree reaches more than 97%, arene content improves 6 percentage points, olefin(e) centent maintains 10% (volume content) in the product gasoline, and improved the content of isoparaffin, be a kind of desirable gasoline hydrogenation modifying desulphurization catalyst.
Claims (4)
1. a deep hydrodesulfurizationsolid solid-acid catalyst of gasoline is characterized in that, is raw material with nickel nitrate, nanometer HZSM-5 zeolite, boehmite (aluminium oxide) and polyoxometallate (POM), and the quality percentage composition of each raw material is as follows:
Nickel nitrate: 0.4～8%
Nanometer HZSM-5 zeolite: 52～80%
Boehmite (aluminium oxide): 15～20%
POM：4～20％。
2. the preparation method of the described a kind of deep hydrodesulfurizationsolid solid-acid catalyst of gasoline of claim 1 is characterized in that, step is as follows:
(1) the nanometer NaZSM-5 of preparation 100nm:
Under normal temperature, normal pressure, the nano-ZSM-5 zeolite sample mixes by 4: 1 mass ratioes with carrier boehmite (aluminium oxide) after burning amine, with the HNO of 10wt%
3Solution bonding and extruded moulding, drying, temperature-programmed calcination makes the nanometer NaZSM-5 of 100nm;
(2) preparation nanometer HZSM-5 zeolite:
With the nanometer NaZSM-5 of the 100nm of step (1) preparation, with the NH of concentration 0.4mol/L
4NO
3Solution normal temperature exchange secondary makes nanometer HZSM-5 zeolite after drying, roasting and 500 ℃ of aqueous vapor passivation again;
(3) preparation NiHZSM-5:
Get nickel nitrate and nanometer HZSM-5 zeolite by the quality percentage composition of the described raw material of claim 1, then nickel nitrate is dissolved in preparation quality concentration in the deionized water and is 10～25% solution, stir and obtain blue settled solution after 5～10 minutes, adopt equi-volume impregnating to be impregnated on the nanometer HZSM-5 of aqueous vapor passivation zeolite, through 100～150 ℃ of oven dry 10～15h, 350～540 ℃ of roasting 3～5h obtain NiHZSM-5;
(4) prepare solid acid catalyst:
Quality percentage composition by the described raw material of claim 1 is got POM, then POM is dissolved in preparation quality concentration in the deionized water and is 10～25% solution, adopt equi-volume impregnating to be impregnated on the NiHZSM-5 then, through 100～150 ℃ of oven dry 10～15h, 350～540 ℃ of roasting 3～5h make solid acid catalyst.
3. the preparation method of a kind of deep hydrodesulfurizationsolid solid-acid catalyst of gasoline according to claim 2 is characterized in that, described sintering temperature is 300～400 ℃.
4. a kind of deep hydrodesulfurizationsolid solid-acid catalyst of gasoline according to claim 1 is characterized in that this catalyst is applied to the gasoline upgrading desulphurization reaction, and reaction temperature is 240～300 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041847A (en) * | 2012-12-25 | 2013-04-17 | 辽宁师范大学 | In-situ synthesized catalyst by polyoxometallate and silicon-containing molecular sieve, as well as preparation method and application of same |
| CN103769202A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Gasoline selective hydro-desulfurization catalyst, preparation method and applications thereof |
| CN103894058A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | Method for removing hydrogen sulfide gas by using polyoxometallate |
| CN104399518A (en) * | 2014-11-11 | 2015-03-11 | 沈阳工业大学 | Preparation method of catalyst for light gasoline catalytic cracking and aromatization |
| CN114073980A (en) * | 2020-08-19 | 2022-02-22 | 中国石油天然气股份有限公司 | Hydrodesulfurization catalyst and preparation method and application thereof |
-
2010
- 2010-01-15 CN CN201010010136A patent/CN101767032A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769202A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Gasoline selective hydro-desulfurization catalyst, preparation method and applications thereof |
| CN103041847A (en) * | 2012-12-25 | 2013-04-17 | 辽宁师范大学 | In-situ synthesized catalyst by polyoxometallate and silicon-containing molecular sieve, as well as preparation method and application of same |
| CN103041847B (en) * | 2012-12-25 | 2015-06-17 | 辽宁师范大学 | In-situ synthesized catalyst by polyoxometallate and silicon-containing molecular sieve, as well as preparation method and application of same |
| CN103894058A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | Method for removing hydrogen sulfide gas by using polyoxometallate |
| CN103894058B (en) * | 2012-12-27 | 2016-06-08 | 中国石油天然气股份有限公司 | Method for removing hydrogen sulfide gas by using polyoxometallate |
| CN104399518A (en) * | 2014-11-11 | 2015-03-11 | 沈阳工业大学 | Preparation method of catalyst for light gasoline catalytic cracking and aromatization |
| CN114073980A (en) * | 2020-08-19 | 2022-02-22 | 中国石油天然气股份有限公司 | Hydrodesulfurization catalyst and preparation method and application thereof |
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