CN102041042B - Inferior wax oil hydrotreating method - Google Patents
Inferior wax oil hydrotreating method Download PDFInfo
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- CN102041042B CN102041042B CN 200910236167 CN200910236167A CN102041042B CN 102041042 B CN102041042 B CN 102041042B CN 200910236167 CN200910236167 CN 200910236167 CN 200910236167 A CN200910236167 A CN 200910236167A CN 102041042 B CN102041042 B CN 102041042B
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000003607 modifier Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 12
- 239000004480 active ingredient Substances 0.000 claims description 11
- 235000003599 food sweetener Nutrition 0.000 claims description 8
- 239000003765 sweetening agent Substances 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910018921 CoO 3 Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 241000282326 Felis catus Species 0.000 claims description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 claims 2
- 150000003961 organosilicon compounds Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 25
- 239000002994 raw material Substances 0.000 abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003223 protective agent Substances 0.000 abstract description 4
- 238000006477 desulfuration reaction Methods 0.000 abstract description 3
- 230000023556 desulfurization Effects 0.000 abstract description 3
- 230000003009 desulfurizing effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004231 fluid catalytic cracking Methods 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000004517 catalytic hydrocracking Methods 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000007921 spray Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 21
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 18
- 239000001993 wax Substances 0.000 description 14
- 238000007598 dipping method Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 9
- 229940010552 ammonium molybdate Drugs 0.000 description 9
- 235000018660 ammonium molybdate Nutrition 0.000 description 9
- 239000011609 ammonium molybdate Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 238000004523 catalytic cracking Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 102000040350 B family Human genes 0.000 description 1
- 108091072128 B family Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for hydrotreating inferior wax oil, which comprises the steps of carrying out hydrogenation treatment at a reaction temperature of 360-380 ℃, a pressure of 8-10.0 MPa, a hydrogen-oil volume ratio of 1000-1500: 1 and a liquid hourly space velocity of 0.5h-1～1.0h-1Hydrotreating the mixture raw material of vacuum gas oil, inferior coker gas oil and deasphalted oil under the condition; the catalyst is prepared by pretreating a macroporous alumina carrier by adopting an organic composite modifier, loading a protective agent, a demetallizing agent, a desulfurizing agent and a denitrifying agent which are prepared by active metal by adopting a primary saturation spray impregnation method, and sequentially grading and filling the protective agent, the demetallizing agent, the desulfurizing agent and the denitrifying agent from top to bottom; the catalyst has the advantages of low reaction temperature, low reaction pressure and high activity, improves the desulfurization rate, the denitrification rate, the residual carbon removal rate and the demetalization rate of the catalyst, and can be directly used as an FCC (fluid catalytic cracking) raw material or a hydrocracking raw material after the raw material is subjected to hydrotreating.
Description
Technical field
The present invention relates to a kind of method of faulty wax oil hydrotreatment, belong to catalyst technical field.
Background technology
Countries in the world petroleum refining industry all is faced with the oil reserved resources and reduces gradually, and oil property is heaviness, poor qualityization day by day.Each oil refining enterprise constantly enlarges the raw material sources of catalytic cracking (FCC) device, and the FCC apparatus raw material mainly is vacuum gas oil (VGO), and the FCC apparatus trend of mixing coking wax oil (CGO) and deasphalted oil inferior raw materials such as (DAO) constantly increases in recent years.
Delayed coking is the important process process of heavy oil lighting in the secondary processing, wax tailings (CGO) is as the maximum cut of coker yield (accounting for 20%～30%), can catalytic cracking mix raw material, but nitrogen, condensed-nuclei aromatics and gum level height in the wax tailings, cracking performance is poor, mix transformation efficiency, gasoline yield and quality product that refining has too much had a strong impact on catalytic cracking, and cause problems such as environmental pollution, make its processing and utilization be subjected to certain limitation.China's grand celebration, the Liaohe River and triumph wax tailings are directly done the highest of catalytically cracked material and are mixed refining than not surpassing 25%, 20% and 18%, even more serious is that a lot of delayed coking units of China are in order to expand production capacity with minimum input, adopt partial circulating than in addition zero circulation recently expand production capacity, cause that wax tailings is more, quality is poorer.
Depend on the pretreated main purpose of hydrogenation for the used catalyzer of FCC raw material hydrogenation pre-treatment.Present most fcc raw material oil hydrogenation pretreatment unit all uses nickel molybdenum catalyst, mainly is in order to reduce nitrogen and the condensed-nuclei aromatics content in the catalysis charging.Demetalization and reduce carbon residue what improve with the raising of hydrogenation pre-treatment severity.
CN200610002376.1 has introduced a kind of method of hydrotreating of producing fine quality catalytic cracking raw material, is characterized in that hydrogenation protecting agent and Hydrodemetalation catalyst are a kind of alumina supporter load molybdenum and/or tungsten, and nickel and/or cobalt.Hydrotreating catalyst is a metal load type catalyst, and carrier is a silica-alumina, and metal component is VI B family or VIII family metal or their combination.It consists of: nickel oxide 1%～10%, and fluorine 1%～10%, phosphorus oxide 0.5%～8%, surplus are silicon oxide and aluminum oxide.
CN200610007532.3 has introduced a kind of method of hydrotreating of producing catalytically cracked material.Be characterized in that hydrogenation protecting agent and residuum hydrogenating and metal-eliminating agent are carrier loaded molybdenum, tungsten, nickel, cobalt reactive metal with aluminum oxide all.The pore size distribution of this carrier be the pore volume of 10～20nm account for total pore volume 70%～98%.The residuum hydrodesulfurization agent is a carrier with aluminum oxide or silicon oxide, load cobalt, molybdenum 8%～20%, nickel, tungsten 0.3%～8% (quality).
The Zhou Yasong of China University Of Petroleum Beijing etc., with the TiO2-SiO2 composite oxides that contain modification HY molecular sieve is carrier, with Ni, W is active metal component, adopt the equal-volume solution dipping method to make coking gas oil hydrotreating catalyst, the Ni-W series catalysts of citric acid modification obviously improves the hydrofining performance of wax tailings, and especially hydrodenitrification performance is greatly improved.But liquid yield descends to some extent.
US4780193 discloses a kind of method of hydrorefining catalyst cracking stock, and this technology adopts hydrorefined method to improve the quality of catalytically cracked material, and its raw material consists of the aromatic hydrocarbons and the naphthenic hydrocarbon of 30% straight-chain paraffin and 70%, and major part is an aromatic hydrocarbons.The temperature of reaction of hydro-refining unit is lower than 390 ℃, and reaction pressure is preferably in more than the 12MPa more than 10MPa.Helping under the saturated and processing condition of aromatic hydrocarbons, improving the cracking performance of catalytic cracking unit raw material, thereby improving the transformation efficiency of catalytic cracking unit, producing low-sulfur content gasoline blend component by hydrofining.The reaction pressure height that this patent requires, relative cost is also high.
Summary of the invention
The objective of the invention is to develop the method for the practicable faulty wax oil hydrotreatment of a cover.
Mainly comprise following several aspect:
(1) preparation of composite modifier
1～5% (quality) cats product, 1～5% (quality) nonionogenic tenside and 1～10% (quality) organoaluminum are dissolved in 60～80% (quality) aqueous ethanolic solution, wherein ethanol accounts for 1～10% (quality), 5～20% (quality) organosilicon is slowly splashed in the above-mentioned solution, 50 ℃～100 constant temperature 0～20 hour, obtain composite modifier.
(2) protectant preparation
After the above-mentioned composite modifier processing of macropore alumina supporter process, after 30 ℃～40 ℃ dryings, under room temperature or heating condition, once be mixed with the aqueous solution of required concentration, wherein MoO with ammonium molybdate, nickelous nitrate
3Concentration is 4g/100ml～10g/100ml, and NiO concentration is 1g/100ml～5g/100ml.Carrier after the dipping active ingredient is at 100 ℃～120 ℃ dry 2h～14h, and calcination process 2h～8h under 400 ℃～600 ℃ air obtains carrier 1～3% (quality) MoO
3With the protective material of 1～2% (quality) NiO, aggregate metal oxide accounts for carrier 2～5% (quality).
(3) preparation of metal remover
At first, after the above-mentioned composite modifier processing of macropore alumina supporter process, after 30 ℃～40 ℃ dryings, under room temperature or heating condition, once be mixed with the aqueous solution of required concentration, wherein MoO with ammonium molybdate, nickelous nitrate
3Concentration is 10g/100ml～30g/100ml, and NiO concentration is 5g/100ml～10g/100ml.Carrier after the dipping active ingredient is at 100 ℃～120 ℃ dry 2h～14h, and roasting place 2h～8h under 400 ℃～600 ℃ air obtains carrier 3～7% (quality) MoO
3With the hydrodemetallation (HDM) agent of 1～3% (quality) NiO, aggregate metal oxide accounts for carrier 4～10% (quality).
(4) preparation of sweetening agent
At first, after the above-mentioned composite modifier processing of macropore alumina supporter process, after 30 ℃～40 ℃ dryings, under room temperature or heating condition, once be mixed with the aqueous solution of required concentration, wherein CoO with Xiao Suangu, ammonium molybdate, nickelous nitrate
3Concentration is 2g/100ml～10g/100ml, MoO
3Concentration is 10g/100ml～20g/100ml, and NiO concentration is 2g/100ml～10g/100ml.Carrier after the dipping active ingredient is at 100 ℃～120 ℃ dry 2h～14h, and roasting place 2h～8h under 400 ℃～600 ℃ air obtains CoO
3, MoO
3With NiO be the sweetening agent of carrier 2～7%, 2～10% and 1～3% (mass ratio), wherein aggregate metal oxide accounts for carrier 5～20% (quality).
(5) preparation of denitrfying agent
At first, after the above-mentioned composite modifier processing of macropore alumina supporter process, after 30 ℃～40 ℃ dryings, under room temperature or heating condition, once be mixed with the aqueous solution of required concentration, wherein WO with ammonium tungstate, ammonium molybdate, nickelous nitrate
3Concentration is 2g/100ml～10g/100ml; MoO
3Concentration is 10g/100ml～20g/100ml; NiO concentration is 2g/100ml～10g/100ml; Carrier after the dipping active ingredient is at 100 ℃～120 ℃ dry 2h～14h, and calcination process 2h～8h under 400 ℃～600 ℃ air obtains WO
3, MoO
3With NiO be the denitrfying agent of carrier 4～11%, 4～15% and 2～4%, wherein aggregate metal oxide accounts for carrier 10～30% (quality).
(6) catalyst activity metal
Employed reactive metal in the preparation steeping fluid process: tungsten can be ammonium tungstate or Tungsten oxide 99.999, and molybdenum can be molybdenum oxide or ammonium molybdate, and nickel can be nickelous nitrate, basic nickel carbonate or nickel oxide, and cobalt is cobalt oxide or Xiao Suangu.More than the different compounds of same metal can substitute mutually.
(7) raw material
Raw material is the mixture of vacuum gas oil (VGO), wax tailings (CGO) and deasphalted oil (DAO), it is characterized in that described raw material is that vacuum gas oil (VGO), wax tailings inferior (CGO) and deasphalted oil (DAO) shared weight percentage in mixture are respectively 40～70% (quality), 0～30% (quality) and 0～30% (quality).
(8) evaluating catalyst
Above-mentioned catalyst combination is at 360 ℃～380 ℃ of temperature of reaction, pressure 8MPa～10.0MPa, hydrogen to oil volume ratio 1000～1500: 1, liquid hourly space velocity 0.5h
-1～1.0h
-1Handle the mixture material of vacuum gas oil (VGO), wax tailings inferior (CGO) and deasphalted oil (DAO) under the condition, have higher desulfurization degree, denitrification percent, take off carbon residue rate, demetallization per.
Beneficial effect
The present invention adopted the composite modifier pre-treatment of the aqueous ethanolic solution preparation of organosilicon and organic surface active agent before the once saturated spray-stain of support of the catalyst.Greatly reduce surface tension through pretreated carrier, when steeping fluid contacts with carrier surface, the organosilicon molecule decomposes gradually, produce a large amount of fresh highly active silicon hydroxyls, be easy to form Me-O-Si-O-Al (Me represents metal) structure at alumina carrier surface, because Si-O key bond distance is greater than Al-O key bond distance, the existence of Si-O key has weakened the interaction force between reactive metal and the alumina supporter, in addition, the existence of organic surface active agent has delayed the hydrolysis rate of organosilicon molecule, weakens the reunion of active metallic ion at carrier surface simultaneously.Carrier is through behind the metallic solution dipping, and catalyst surface generates a large amount of nano level silicon oxide in roasting process, produces sterically hinderedly, suppresses the generation of reactive metal agglomeration at high temperature greatly.
Therefore, this preparation method improved metal active constituent dispersion state and and carrier interactions, thereby the utilising efficiency that improves active ingredient improves activity of such catalysts.
Embodiment
Enumerate embodiment below, the present invention is further specified, but the present invention is not only limited to following examples.
Embodiment 1
(1) preparation of support of the catalyst
It is material that support of the catalyst adopts pseudo-boehmite (mass content 95%), sesbania powder (mass content 2%) and aqueous nitric acid (mass content 3%), by drying behind the extruded moulding, obtain the cloverleaf pattern macropore alumina supporter 500 ℃～1000 ℃ following roastings.
(2) preparation of composite modifier
5% (quality) cetyl trimethylammonium bromide, 3% (quality) Triton X-100 (OP-10) and 2% (quality) aluminum isopropylate are dissolved in 80% (quality) aqueous ethanolic solution, wherein ethanol accounts for 2% (quality), with 10% (quality) tetraethoxy (TEOS) with slowly splash in the above-mentioned solution, 80 ℃ of constant temperature 5 hours obtains composite modifier.
(3) protectant preparation
After the above-mentioned composite modifier processing of macropore alumina supporter process, after 30 ℃～40 ℃ dryings, under room temperature or heating condition, once be mixed with the aqueous solution of required concentration, wherein MoO with ammonium molybdate, nickelous nitrate
3Concentration is 8g/100ml, and NiO concentration is 4g/100ml.Carrier after the dipping active ingredient is at 100 ℃～120 ℃ dry 2h～14h, and calcination process 2h～8h under 400 ℃～600 ℃ air obtains containing 3% (quality) MoO
3Protective material with 1% (quality) NiO.Aggregate metal oxide accounts for 4% (quality).
(4) preparation of hydrodemetallation (HDM) agent
At first, after the above-mentioned composite modifier processing of macropore alumina supporter process, after 30 ℃～40 ℃ dryings, under room temperature or heating condition, once be mixed with the aqueous solution of required concentration, wherein MoO with ammonium molybdate, nickelous nitrate
3Concentration is 20g/100ml; NiO concentration is 8g/100ml; Carrier after the dipping active ingredient is at 100 ℃～120 ℃ dry 2h～14h, and calcination process 2h～8h under 400 ℃～600 ℃ air obtains containing 6% (quality) MoO
3With the hydrodemetallation (HDM) agent of 2% (quality) NiO, aggregate metal oxide accounts for 8% (quality).
(5) preparation of sweetening agent
At first, after the above-mentioned composite modifier processing of macropore alumina supporter process, after 30 ℃～40 ℃ dryings, under room temperature or heating condition, once be mixed with the aqueous solution of required concentration, wherein CoO with Xiao Suangu, ammonium molybdate, nickelous nitrate
3Concentration is 10g/100ml; MoO
3Concentration is 15g/100ml; NiO concentration is 5g/100ml; Carrier after the dipping active ingredient is at 110 ℃ of dry 10h, and calcination process 6h under 500 ℃ of air obtains CoO
3: MoO
3: NiO=8%: the sweetening agent of 8%: 2% (quality), wherein aggregate metal oxide accounts for 18% (quality).
(6) preparation of denitrfying agent
At first, after the above-mentioned composite modifier processing of macropore alumina supporter process, after 30 ℃～40 ℃ dryings, under room temperature or heating condition, once be mixed with the aqueous solution of required concentration, wherein WO with ammonium tungstate, ammonium molybdate, nickelous nitrate
3Concentration is 7g/100ml; MoO
3Concentration is 14g/100ml; NiO concentration is 4g/100ml; Carrier after the dipping active ingredient is at 110 ℃ of dry 10h, and calcination process 6h under 500 ℃ of air obtains WO
3: MoO
3: NiO=10%: the denitrfying agent of 12%: 3% (quality), wherein aggregate metal oxide accounts for 25% (quality).
(7) character of the protective material of above preparation, metal remover, sweetening agent, denitrfying agent is as shown in table 1, selects inferior raw material (quality VGO: CGO: DAO=2: 1: 1) for raw material carries out the catalyst hydrogenation evaluation, and feedstock property is as shown in table 2.At 370 ℃ of temperature of reaction, reaction pressure 8.0MPa, hydrogen to oil volume ratio 1000: 1, volume space velocity 1.0h
-1Processing condition under, evaluation result sees Table 3 embodiment 1, desulfurization degree 90%, denitrification percent 75%, takes off carbon residue rate 83%, metal removal rate 81.8%.Obtain the comparative catalyst according to patent CN101007964A preparation method, comparative catalyst's evaluation result sees Table 3, catalyst desulfurizing rate, the denitrification percent of present method preparation, take off the carbon residue rate, the demetallization per comparison all increases than catalyzer, especially denitrification percent significantly improves 5%.
Table 1 faulty wax oil hydrotreating catalyst
Table 2 faulty wax oil feedstock property
Table 3 catalyst hydrogenation comparative evaluation
Claims (1)
1. the method for a faulty wax oil hydrotreatment is characterized in that: at 360 ℃～380 ℃ of temperature of reaction, pressure 8MPa～10.0MPa, hydrogen to oil volume ratio 1000～1500:1, liquid hourly space velocity 0.5h
-1～1.0h
-1The mixture material of hydrotreatment vacuum gas oil, wax tailings inferior and deasphalted oil under the condition;
Catalyzer is by adopting organic composite modifier to the macropore alumina supporter pre-treatment, adopt once protective material, metal remover, sweetening agent and the denitrfying agent of the method supported active metal preparation of saturated spray-stain, by the order grading loading that is followed successively by protective material, metal remover, sweetening agent and denitrfying agent from top to bottom;
By mass percentage, the synthetic of organic composite modifier is that 1～5% cats product, 1～5% nonionogenic tenside and 1～10% organoaluminum are dissolved in 60～80% aqueous ethanolic solutions, the ethanol quality is 1～10% in the aqueous ethanolic solution, slowly splash into 5～20% organosilicons in the solution, 50 ℃～100 ℃ constant temperature 0～20 hour, obtain composite modifier;
Macropore alumina supporter adopts once the method for saturated spray-stain to be prepared as carrier quality 1～3%MOO through after the described composite modifier pre-treatment
3Protective material with 1～2%NiO;
Macropore alumina supporter adopts once the method for saturated spray-stain to be prepared as carrier quality 3～7%MoO through after the described composite modifier pre-treatment
3Metal remover with 1～3%NiO;
Macropore alumina supporter is an active ingredient with Co-Mo-Ni after handling through described composite modifier, and once the method for saturated spray-stain prepares sweetening agent, by quality CoO
3, MoO
3Be respectively carrier quality 2～7%, 2～10% and 1～3% with NiO;
After macropore alumina supporter was handled through described composite modifier, employing W-Mo-Ni was an active ingredient, and once the method for saturated spray-stain prepares denitrfying agent, by quality WO
3, MoO
3Be respectively carrier quality 4～11%, 4～15% and 2～4% with NiO.
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| CN102899081B (en) * | 2011-07-28 | 2015-03-18 | 中国石油化工股份有限公司 | Wax oil hydrotreating method |
| CN103184070B (en) * | 2011-12-28 | 2015-07-29 | 中国石油天然气股份有限公司 | Method for removing nitride from inferior coker gas oil |
| CN103184069B (en) * | 2011-12-28 | 2015-01-21 | 中国石油天然气股份有限公司 | Inferior coker gas oil hydrotreating method |
| CN104549536B (en) * | 2013-10-23 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of preprocess method of alumina support |
| CN105983416A (en) * | 2015-02-10 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method and application of catalytic cracking raw material hydrodenitrogenation catalyst |
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| CN1362481A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Catalyst sorting and loading method |
| CN1488719A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Heavy hydrocarbon hydroprocessing method |
| CN1769384A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Heavy distillate oil hydrogenation catalyst and its preparation method |
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| CN1362481A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Catalyst sorting and loading method |
| CN1488719A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Heavy hydrocarbon hydroprocessing method |
| CN1769384A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Heavy distillate oil hydrogenation catalyst and its preparation method |
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