CN102658142A - Residual oil hydrogenation catalyst oolitic stones and method for obtaining light oil and vanadium from Tahe residue oil - Google Patents
Residual oil hydrogenation catalyst oolitic stones and method for obtaining light oil and vanadium from Tahe residue oil Download PDFInfo
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- CN102658142A CN102658142A CN2012101178125A CN201210117812A CN102658142A CN 102658142 A CN102658142 A CN 102658142A CN 2012101178125 A CN2012101178125 A CN 2012101178125A CN 201210117812 A CN201210117812 A CN 201210117812A CN 102658142 A CN102658142 A CN 102658142A
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 45
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000004575 stone Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 title abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 6
- 238000002386 leaching Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000012216 screening Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000004227 thermal cracking Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 23
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 22
- 239000002956 ash Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- 101710089042 Demethyl-4-deoxygadusol synthase Proteins 0.000 claims description 14
- 238000011010 flushing procedure Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 238000011978 dissolution method Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- XGZRAKBCYZIBKP-UHFFFAOYSA-L disodium;dihydroxide Chemical compound [OH-].[OH-].[Na+].[Na+] XGZRAKBCYZIBKP-UHFFFAOYSA-L 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000005261 decarburization Methods 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 98
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000032696 parturition Effects 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YNZSKFFENDBGOV-UHFFFAOYSA-N [V].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [V].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YNZSKFFENDBGOV-UHFFFAOYSA-N 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical class O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012053 oil suspension Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses residual oil hydrogenation catalyst oolitic stones and a method for obtaining light oil and vanadium from Tahe residue oil. The residual oil hydrogenation catalyst oolitic stones are obtained through the following steps: step 1, oolitic stone material screening, step 2, washing, step 3, drying, and step 4, calcination. The method for obtaining light oil and vanadium from Tahe residue oil comprises the steps as follows: in the first step, catalytic hydrogenation thermal cracking is performed; in the second step, reaction products are separated; in the third step, residues are processed through roasting and decarburization; in the fourth step, an alkali solution method is adopted for leaching; in the fifth step, precipitation is carried out; and in the sixth step, orange powdered V2O5 is obtained after decomposition is performed. The oolitic stone material of the obtained residual oil hydrogenation catalyst oolitic stones belongs to natural inorganic minerals, and has wide sources; the production method and the processing procedure of the residual oil hydrogenation catalyst oolitic stones are very simple; the method for obtaining light oil and vanadium from Tahe residue oil achieves mild conditions and simple steps, so that the cost is lower, and the recovery rate is higher; and therefore, the resources of Tahe residue oil can be utilized fully and advantageously.
Description
Technical field
the present invention relates to residual oil hydrocatalyst and from residual oil, obtain the technical field of light oil and vanadium, are a kind of residual oil hydrocatalyst oolith stone and the method that from Tahe residual oil, obtains light oil and vanadium.
Background technology
Tahe residual oil has that lower H/C is bigger than, viscosity, sulphur and asphalt content is high, tenor characteristics such as content of vanadium height particularly, belongs to a kind of poor residuum that is difficult to secondary operations.Because of the existence of metallic element vanadium can cause catalyst poisoning, cause the catalysis processing technology to be difficult to carry out.Adopt hot-working, yield of light oil is low, and oil quality is poor.Thereby Tahe residual oil generally is used for producing road asphalt, has caused the wasting of resources.
Ren Zhendong etc. are in petroleum technology and application (2006; 24 (3): disclose following content in hydrocracking one literary composition of the normal slag of the Tahe of 202-205) delivering under the oil-soluble molybdenum catalyst: adopt oil-soluble disperse type catalyzer research Tahe reduced crude hydrocracking reaction; Under 430 ℃; The hydrogen first pressing is 7.0 MPa, and bottoms conversion is difficult to reach 60%, and the total recovery of petrol and diesel oil is up to 33.2wt%.
Tao Yang is at the 9th the academic nd Annual Meeting collection (2005 of national chemical technology; Following content is disclosed in Tahe dreg-oil suspension bed hydrogenation cracking technical study one literary composition of 1271-1273) delivering: adopt molybdenum, nickel water soluble metal catalyst; Reaction pressure is up to 14 MPa, and the highest yield of≤350 ℃ light oil is 31.6wt%.
The trace vanadium that exists in
oil causes its viscosity significantly to increase, and association has taken place for vfanadium compound and asphalt in the oil, has formed asphalitine gummed ion.Disclose following content in the separation of Zhou Aihui vfanadium compound in the Tahe reduced crude that China Petroleum Univ. (East-China) 2011 delivers, purification and evaluation one literary composition: vanadium is in colloid and bitum three-dimensional structure; Have only the destruction three-dimensional structure, just can discharge micromolecular vfanadium compound.Therefore, adopt processing modes such as common heating or stirring, can not it removed and reclaim.
patent No. is US4; 116; 820 american documentation literature discloses following content: handle residual oil with sour modified activated carbon down at high temperature (370～450 ℃), the active carbon aperture is between 1～10 nm, and the vanadium in the heavy oil removes more than 80%.Liu Zhangyong is in China University Of Petroleum Beijing. and the 2010 residual oil reaction-absorption demetalizations delivered are studied and are disclosed following content in the literary composition: adopt the sour modified kaolin of sour modification, nickel-loaded and load molybdenum Liaohe River reduced crude and Tahe decompression residuum are carried out the HDM reaction, studied the distribution of nickel, vanadium in the product and had form.The patent No. is that the Russ P document of 2998578/23-04 (1982.08.23) discloses following content: that use to produce titanium-aluminium alloy contains the aluminum oxide waste material, and it consists of 0.3～3.0% aluminium oxide, 0.3～1.0% iron oxide; 2.0～4.0% titanium dioxide; All the other are silica, under 20～35 ℃, and the part vanadium porphyrin complex in the adsorbing and extracting crude oil; The dosage of adsorbent is 8～10%, and the recovery rate of vanadium porphyrin complex is 97.2～98%.
are visible, and the Tahe residual hydrocracking exists not enough, and reactive hydrogen first pressing or reaction pressure are bigger, and yield of light oil is not high.The content of this asphaltene in vacuum residues is 21.8%, and vanadium concentration is 307 gram/tons, and the vanadium apportionment ratio in the asphalitine is 87.9%, processing refining difficulty.
Summary of the invention
the present invention provides a kind of residual oil hydrocatalyst oolith stone and from Tahe residual oil, obtains the method for light oil and vanadium; Overcome the deficiency of prior art; Light oil and vanadium have been realized from Tahe residual oil, obtaining; And cost is low, the rate of recovery is high, thereby has made full use of Tahe residual oil resource.
One of technical scheme of the present invention obtains in the following manner: a kind of residual oil hydrocatalyst oolith stone, and it obtains by following step:
First step screening: from the raw ore of oolith stone, filter out Fe
2
O
3
, SiO
2
And Al
2
O
3
Content is respectively 60～70wt%, 6～18wt% and 2～8wt%, diameter is the oolith shape ore of 0.2～2 mm;
Second step flushing: clean with distilled water flushing;
The 3rd step is dry: dried by the fire 30 minutes to 60 minutes down at 150 ± 10 ℃;
the 4th step calcining: calcined 1 hour to 2 hours down at 600 ± 10 ℃, obtain residual oil hydrocatalyst oolith stone.
Two of technical scheme of the present invention obtains in the following manner: a kind of production method of residual oil hydrocatalyst oolith stone is characterized in that being undertaken by following step:
First step screening: from the raw ore of oolith stone, filter out Fe
2
O
3
, SiO
2
And Al
2
O
3
Content is respectively 60～70wt%, 6～18wt% and 2～8wt%, diameter is the oolith shape ore of 0.2～2 mm;
Second step flushing: clean with distilled water flushing;
The 3rd step is dry: dried by the fire 30 minutes to 60 minutes down at 150 ± 10 ℃;
the 4th step calcining: calcined 1 hour to 2 hours down at 600 ± 10 ℃, obtain residual oil hydrocatalyst oolith stone.
Three of technical scheme of the present invention obtains in the following manner: a kind of method that from Tahe residual oil, obtains light oil and vanadium of utilizing above-mentioned residual oil hydrocatalyst oolith stone, and it is undertaken by following step:
First step catalytic hydrogenation thermal cracking: add the proportioning of residual oil hydrocatalyst oolith stone 1.0～2.0 g by per 50 g residual oil, will
Residual oil Join in the stirring sealed reactor with residual oil hydrocatalyst oolith stone, logical purity does in still
99.99%Hydrogen exchange 3 times to 5 times, be pressurized to 1.0 MPa to 6.0 MPa then, mixing speed is 300 r/min to 350 r/min; Control 2 ℃ of programming rates/min to 10 ℃/min; Be heated to reaction temperature, this temperature is 380 ℃ to 430 ℃, isothermal reaction 15 min to 120 min; After reaction finishes, be cooled to room temperature, take out product;
The second step product is separated: with the product that the above-mentioned first step obtains, carry out cable-styled extracting with n-hexane and toluene successively, obtain light oil, asphalitine, residue respectively;
Charcoal is taken off in the 3rd step residue roasting: the residue that second step was obtained makes vanadium metal change V into 550 ± 10 ℃ of following roastings till all being converted into ashes
2
O
5
;
The 4th step alkali dissolution method leaching:, add the above-mentioned the 3rd and go on foot the ashes that obtain and make the V in the ashes with an amount of NaOH NaOH aqueous solution that obtains soluble in water
2
O
5
All dissolving and filtration obtain filtrating;
The 5th step deposition: the filtrating that the 4th step was obtained maintains 30 ℃ to 50 ℃; To add mass percent concentration by every 5.0g ashes component be 50%～60% ammonium chloride solution, 7 mL～10 mL, splash into 50mg/L～150 mg/L ammonium metavanadate solutions, 0.1 mL～0.5 mL; Left standstill 1 day～2 days, and white precipitate occurred;
The 6th step decomposed: the product that the 5th step was obtained carries out suction filtration, then drying precipitate and roasting is obtained orange-yellow Powdered V
2
O
5
Be three further optimization and/or selection below to technique scheme:
In above-mentioned the 4th step, an amount of NaOH is for making V
2
O
5
All dissolving and pH value of solution value are till between 8 to 9.
above-mentioned the 4th the step in, with the 3rd the step ashes progressively be added in the sodium hydroxide solution, boiled 1 hour to 2 hours.
In above-mentioned the 6th step; Vacuum is 0.01～0.02 MPa, with 1～2% ammonium chloride solution, 20～30 mL washing leaching cakes 3～5 times, will be deposited in 105 ℃ of bakings after 1 hour～2 hours down then; 475 ± 10 ℃ of following roastings 3 hours～5 hours, just obtain orange-yellow Powdered V again
2
O
5
Cable-styled extracting with the product of the first step, is carried out with n-hexane and toluene successively in
in above-mentioned second step, extraction temperature is respectively 110 ℃ and 150 ℃, and the extracting time is 72 hours～and 96 hours; Wherein, the n-hexane DDGS is defined as oil, and n-hexane insoluble matter toluene DDGS is an asphalitine, and toluene insolubles is a residue, and the n-hexane DDGS of boiling point≤350 ℃ is that light oil is defined as light oil.
The invention has the beneficial effects as follows:
⑴ Tahe residual oil catalytic pyrolysis is handled, and getting oily yield is 49.8～76.6%, and giving birth to the slag rate is 7.9～27.5%, and the apportionment ratio of vanadium in residue is 50.1～99.3%.
⑵ is 2.0% at oolith stone dosage, reaction temperature is that 425 ℃, hydrogen first pressing are that 3.0 MPa and reaction time are under the condition of 45 min, and oily yield is 61.29%, and yield of light oil is 50.1%; Giving birth to the slag rate is 20.32%, and the apportionment ratio of vanadium in residue is 95.55%.
⑶ adopt the V in the disposable leaching ashes of alkali dissolution method
2
O
5
, Jin Chushuai>96wt%.To precipitate the V that the ammonium metavanadate roasting obtains
2
O
5
Purity is high.From residual oil, reclaim vanadium, overall recovery reaches 91.7wt%.
therefore, the raw material oolith stone of gained residual oil hydrocatalyst oolith stone of the present invention belongs to natural inorganic mineral, wide material sources; The production method processing procedure of residual oil hydrocatalyst oolith stone of the present invention is very simple; The present invention obtains the method for light oil and vanadium from Tahe residual oil, mild condition, step are simple, thereby cost is lower, and the rate of recovery is higher; Thereby help making full use of of Tahe residual oil resource.
The specific embodiment
the present invention does not receive the restriction of following embodiment, can confirm concrete embodiment according to the technical scheme and the actual conditions of the invention described above.
Below in conjunction with embodiment the present invention is done further argumentation:
Embodiment 1, and this residual oil hydrocatalyst oolith stone obtains by following step:
First step screening: from the raw ore of oolith stone, filter out Fe
2
O
3
, SiO
2
And Al
2
O
3
Content is respectively 60～70wt%, 6～18wt% and 2～8wt%, diameter is the oolith shape ore of 0.2～2 mm;
Second step flushing: clean with distilled water flushing;
The 3rd step is dry: dried by the fire 30 minutes to 60 minutes down at 150 ± 10 ℃;
the 4th step calcining: calcined 1 hour to 2 hours down at 600 ± 10 ℃, obtain residual oil hydrocatalyst oolith stone.
Embodiment 2, and this residual oil hydrocatalyst oolith stone obtains by following step:
First step screening: from the raw ore of oolith stone, filter out Fe
2
O
3
, SiO
2
And Al
2
O
3
Content is respectively 60 wt% or 70wt%, 6wt% or 18wt%, 2wt% or 8wt%, diameter is the oolith shape ore of 0.2 mm or 2 mm;
Second step flushing: clean with distilled water flushing;
The 3rd step is dry: dried by the fire 30 minutes or 60 minutes down at 140 ℃ or 160 ℃;
the 4th step calcining: calcined 1 hour or 2 hours down at 590 ℃ or 610 ℃, obtain residual oil hydrocatalyst oolith stone.
Embodiment 3, and the method that should from Tahe residual oil, obtain light oil and vanadium is undertaken by following step:
First step catalytic hydrogenation thermal cracking: add the proportioning of residual oil hydrocatalyst oolith stone (embodiment 1 or embodiment 2) 1.0～2.0g by per 50 g residual oil, will
Residual oil Join in the stirring sealed reactor with residual oil hydrocatalyst oolith stone, logical purity does in still
99.99% (percent by volume)Hydrogen exchange 3 times to 5 times, be pressurized to 1.0 MPa to 6.0 MPa then, mixing speed is 300r/min to 350r/min; Control 2 ℃ of programming rates/min to 10 ℃/min; Be heated to reaction temperature, this temperature is 380 ℃ to 430 ℃, isothermal reaction 15 min to 120 min; After reaction finishes, be cooled to room temperature, take out product;
The second step product is separated: with the product that the above-mentioned first step obtains, carry out cable-styled extracting with n-hexane and toluene successively, obtain light oil, asphalitine, residue respectively;
Charcoal is taken off in the 3rd step residue roasting: the residue that second step was obtained makes vanadium metal change V into 550 ± 10 ℃ of following roastings till all being converted into ashes
2
O
5
;
The 4th step alkali dissolution method leaching:, add the above-mentioned the 3rd and go on foot the ashes that obtain and make the V in the ashes with an amount of NaOH NaOH aqueous solution that obtains soluble in water
2
O
5
All dissolving and filtration obtain filtrating;
The 5th step deposition: the filtrating that the 4th step was obtained maintains 30 ℃ to 50 ℃; To add mass percent concentration by per 5.0 g ashes components be 50%～60% ammonium chloride solution, 7 mL～10 mL, splash into 50mg/L～150 mg/L ammonium metavanadate solutions, 0.1 mL～0.5 mL; Left standstill 1 day～2 days, and white precipitate occurred;
The 6th step decomposed: the product that the 5th step was obtained carries out suction filtration, then drying precipitate and roasting is obtained orange-yellow Powdered V
2
O
5
Embodiment 4, and the method that should from Tahe residual oil, obtain light oil and vanadium is undertaken by following step:
First step catalytic hydrogenation thermal cracking: add the proportioning of residual oil hydrocatalyst oolith stone (embodiment 1 or embodiment 2) 1.0g or 2.0 g by every 50g residual oil, will
Residual oil Join in the stirring sealed reactor with residual oil hydrocatalyst oolith stone, logical purity does in still
99.99% (percent by volume)Hydrogen exchange 3 times or 5 times, be pressurized to 1.0 MPa or 6.0 MPa then, mixing speed is 300r/min or 350r/min; Control 2 ℃/min of programming rate or 10 ℃/min; Be heated to reaction temperature, this temperature is 380 ℃ or 430 ℃, isothermal reaction 15 min or 120 min; After reaction finishes, be cooled to room temperature, take out product;
The second step product is separated: with the product that the above-mentioned first step obtains, carry out cable-styled extracting with n-hexane and toluene successively, obtain oil, asphalitine, residue respectively;
Charcoal is taken off in the 3rd step residue roasting: the residue that second step was obtained makes vanadium metal change V into 540 ℃ or 560 ℃ of following roastings till all being converted into ashes
2
O
5
;
The 4th step alkali dissolution method leaching:, add the above-mentioned the 3rd and go on foot the ashes that obtain and make the V in the ashes with an amount of NaOH NaOH aqueous solution that obtains soluble in water
2
O
5
All dissolving and filtration obtain filtrating;
The 5th step deposition: the filtrating that the 4th step was obtained maintains 30 ℃ or 50 ℃; Adding mass percent concentration by every 5.0g ashes component is 50% or 60% ammonium chloride solution 7 mL or 10 mL, splashes into 50mg/L or 150 mg/L ammonium metavanadate solutions, 0.1 mL or 0.5 mL; Left standstill 1 day or 2 days, and separated out a large amount of white precipitates;
The 6th step decomposed: the product that the 5th step was obtained carries out suction filtration, then drying precipitate and roasting is obtained orange-yellow Powdered V
2
O
5
Embodiment 5, are with the difference of embodiment 3 and 4: in the 4th step of embodiment 5, an amount of NaOH is for making V
2
O
5
All dissolving and pH value of solution value are till between 8 to 9.
Embodiment 6, are with the difference of embodiment 3 and 4: in the 4th step of embodiment 6, an amount of NaOH is for making V
2
O
5
All dissolving and pH value of solution value are till between 8 to 9.
embodiment 7 is with the difference of embodiment 3 to 6: in the 4th step of embodiment 7, the ashes in the 3rd step progressively are added in the sodium hydroxide solution, boiled 1 hour to 2 hours.
embodiment 8 is with the difference of embodiment 3 to 6: in the 4th step of embodiment 8, the ashes in the 3rd step progressively are added in the sodium hydroxide solution, boiled 1 hour or 2 hours.
Embodiment 9; Be with the difference of embodiment 3 to 8: in the 6th step of embodiment 9; Vacuum is 0.01～0.02 MPa, and using mass percent concentration is 1～2% ammonium chloride solution, 20～30 mL washing leaching cakes 3～5 times, will be deposited in 105 ℃ then and dry by the fire after 1 hour～2 hours down; 475 ± 10 ℃ of following roastings 3 hours～5 hours, just obtain orange-yellow Powdered V again
2
O
5
Finished product.
Embodiment 10; Be with the difference of embodiment 3 to 8: in the 6th step of embodiment 10; Vacuum is 0.01MPa or 0.02 MPa, and using mass percent concentration is 1% or 2% ammonium chloride solution, 20 mL or 30 mL washing leaching cakes 3 times or 5 times, will be deposited in 105 ℃ of bakings after 1 hour or 2 hours down then; 465 ℃ or 485 ℃ of following roastings 3 hours or 5 hours, just obtain orange-yellow Powdered V again
2
O
5
In the above-described embodiments:
Product yield calculates:
The quality of residual oil is designated as m
Residual oil
, the quality of n-hexane DDGS is m
Oil
, the quality of n-hexane insoluble matter toluene DDGS is m
Asphalitine
, the quality of toluene insolubles is m
Residue
, the quality of≤350 ℃ light oil is m
Light oil
1. gas productive rate, %=[(m
Residual oil
-m
Oil
-m
Asphalitine
-m
Residue
)/m
Residual oil
] * 100%
2. oily yield, %=[m
Oil
/ m
Residual oil
] * 100%
3. asphalitine yield, %=[m
Asphalitine
/ m
Residual oil
] * 100%
4. give birth to slag rate, %=[m
Residue
/ m
Residual oil
] * 100%
5. yield of light oil, %=[m
Light oil
/ m
Residual oil
] * 100%
The vanadium apportionment ratio calculates:
are with the vanadium concentration in tannic acid-TGA spectrophotometry residual oil, oil and the asphalitine.Vanadium concentration in the residual oil is c
Residual oil
, the vanadium concentration in the oil is c
Oil
, the vanadium concentration in the asphalitine is c
Asphalitine
Calculate the vanadium apportionment ratio η in fuel-displaced, asphalitine and the residue.
1. η
Oil
, %=[(m
Oil
* c
Oil
)/(m
Residual oil
* c
Residual oil
)] * 100%
2. η
Asphalitine
, %=[(m
Asphalitine
* c
Asphalitine
)/(m
Residual oil
* c
Residual oil
)] * 100%
3. η
Residue
, %=[100-η
Oil
-η
Asphalitine
] %
Through following result is measured and calculated to the foregoing description:
⑴ Tahe residual oil catalytic pyrolysis is handled, and getting oily yield is 49.8～76.6%, and giving birth to the slag rate is 7.9～27.5%, and the apportionment ratio of vanadium in residue is 50.1～99.3%.
⑵ is 2.0% at oolith stone dosage, reaction temperature is that 425 ℃, hydrogen first pressing are that 3.0 MPa and reaction time are under the condition of 45 min, and oily yield is 61.29%, and yield of light oil is 50.1%; Giving birth to the slag rate is 20.32%, and the apportionment ratio of vanadium in residue is 95.55%.
⑶ adopt the V in the disposable leaching ashes of alkali dissolution method
2
O
5
, Jin Chushuai>96wt%.To precipitate the V that the ammonium metavanadate roasting obtains
2
O
5
Purity is high.From residual oil, reclaim vanadium, overall recovery reaches 91.7wt%.
Claims (10)
1. residual oil hydrocatalyst oolith stone is characterized in that obtaining by following step:
First step screening: from the raw ore of oolith stone, filter out Fe
2O
3, SiO
2And Al
2O
3Content is respectively 60～70wt%, 6～18wt% and 2～8wt%, diameter is the oolith shape ore of 0.2～2 mm;
Second step flushing: clean with distilled water flushing;
The 3rd step is dry: dried by the fire 30 minutes to 60 minutes down at 150 ± 10 ℃;
The 4th step calcining: calcined 1 hour to 2 hours down at 600 ± 10 ℃, obtain residual oil hydrocatalyst oolith stone.
2. the production method of a residual oil hydrocatalyst oolith stone is characterized in that being undertaken by following step:
First step screening: from the raw ore of oolith stone, filter out Fe
2O
3, SiO
2And Al
2O
3Content is respectively 60～70wt%, 6～18wt% and 2～8wt%, and diameter is the oolith shape ore of 0.2～2 mm;
Second step flushing: clean with distilled water flushing;
The 3rd step is dry: dried by the fire 30 minutes to 60 minutes down at 150 ± 10 ℃;
The 4th step calcining: calcined 1 hour to 2 hours down at 600 ± 10 ℃, obtain residual oil hydrocatalyst oolith stone.
3. one kind is utilized the acquisition light oil from Tahe residual oil of the said residual oil hydrocatalyst oolith of claim 1 stone and the method for vanadium, it is characterized in that being undertaken by following step:
First step catalytic hydrogenation thermal cracking: add the proportioning of residual oil hydrocatalyst oolith stone 1.0～2.0 g by per 50 g residual oil, will
Residual oil Join in the stirring sealed reactor with residual oil hydrocatalyst oolith stone, logical purity does in still
99.99%Hydrogen exchange 3 times to 5 times, be pressurized to 1.0 MPa to 6.0 MPa then, mixing speed is 300 r/min to 350 r/min; Control 2 ℃ of programming rates/min to 10 ℃/min; Be heated to reaction temperature, this temperature is 380 ℃ to 430 ℃, isothermal reaction 15 min to 120 min; After reaction finishes, be cooled to room temperature, take out product;
The second step product is separated: with the product that the above-mentioned first step obtains, carry out cable-styled extracting with n-hexane and toluene successively, obtain oil, asphalitine, residue respectively;
Charcoal is taken off in the 3rd step residue roasting: the residue that second step was obtained makes vanadium metal change V into 550 ± 10 ℃ of following roastings till all being converted into ashes
2O
5;
The 4th step alkali dissolution method leaching:, add the above-mentioned the 3rd and go on foot the ashes that obtain and make the V in the ashes with an amount of NaOH NaOH aqueous solution that obtains soluble in water
2O
5All dissolving and filtration obtain filtrating;
The 5th step deposition: the filtrating that the 4th step was obtained maintains 30 ℃ to 50 ℃; To add mass percent concentration by every 5.0g ashes component be 50%～60% ammonium chloride solution, 7 mL～10 mL, splash into 50mg/L～150 mg/L ammonium metavanadate solutions, 0.1 mL～0.5 mL; Left standstill 1 day～2 days, and white precipitate occurred;
The 6th step decomposed: the product that the 5th step was obtained carries out suction filtration, then drying precipitate and roasting is obtained orange-yellow Powdered V
2O
5
4. the method that from Tahe residual oil, obtains light oil and vanadium according to claim 3 is characterized in that in the 4th step, an amount of NaOH is for making V
2O
5All dissolving and pH value of solution value are till between 8 to 9.
5. according to claim 3 or the 4 described methods that from Tahe residual oil, obtain light oil and vanadium, it is characterized in that in the 4th step, the 3rd ashes that go on foot progressively are added in the sodium hydroxide solution, boiled 1 hour to 2 hours.
6. according to claim 3 or the 4 described methods that from Tahe residual oil, obtain light oil and vanadium; It is characterized in that in the 6th step; Vacuum is 0.01～0.02 MPa, with 1～2% ammonium chloride solution, 20～30 mL washing leaching cakes 3～5 times, will be deposited in 105 ℃ of bakings after 1 hour～2 hours down then; 475 ± 10 ℃ of following roastings 3 hours～5 hours, just obtain orange-yellow Powdered V again
2O
5
7. the method that from Tahe residual oil, obtains light oil and vanadium according to claim 5; It is characterized in that in the 6th step; Vacuum is 0.01～0.02 MPa, with 1～2% ammonium chloride solution, 20～30 mL washing leaching cakes 3～5 times, will be deposited in 105 ℃ of bakings after 1 hour～2 hours down then; 475 ± 10 ℃ of following roastings 3 hours～5 hours, just obtain orange-yellow Powdered V again
2O
5
8. according to claim 3 or the 4 described methods that from Tahe residual oil, obtain light oil and vanadium; It is characterized in that in second step; Product with the first step; Carry out cable-styled extracting with n-hexane and toluene respectively, extraction temperature is respectively 110 ℃ and 150 ℃, and the extracting time is 72 hours～and 96 hours; Wherein, the n-hexane DDGS is defined as oil, and n-hexane insoluble matter toluene DDGS is an asphalitine, and toluene insolubles is a residue, and the n-hexane DDGS of boiling point≤350 ℃ is that light oil is defined as light oil.
9. the method that from Tahe residual oil, obtains light oil and vanadium according to claim 5; It is characterized in that with the product of the first step, carrying out cable-styled extracting with n-hexane and toluene successively in second step; Extraction temperature is respectively 110 ℃ and 150 ℃, and the extracting time is 72 hours～and 96 hours; Wherein, the n-hexane DDGS is defined as oil, and n-hexane insoluble matter toluene DDGS is an asphalitine, and toluene insolubles is a residue, and the n-hexane DDGS of boiling point≤350 ℃ is that light oil is defined as light oil.
10. the method that from Tahe residual oil, obtains light oil and vanadium according to claim 7; It is characterized in that with the product of the first step, carrying out cable-styled extracting with n-hexane and toluene successively in second step; Extraction temperature is respectively 110 ℃ and 150 ℃, and the extracting time is 72 hours～and 96 hours; Wherein, the n-hexane DDGS is defined as oil, and n-hexane insoluble matter toluene DDGS is an asphalitine, and toluene insolubles is a residue, and the n-hexane DDGS of boiling point≤350 ℃ is that light oil is defined as light oil.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105648220A (en) * | 2016-02-03 | 2016-06-08 | 台州天天环保科技有限公司 | Technology for recycling vanadium from hydrogenation tail oil of suspended bed |
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|---|---|---|---|---|
| US4116820A (en) * | 1977-06-29 | 1978-09-26 | Shell Oil Company | Process for demetallizing of heavy hydrocarbons |
| US5474977A (en) * | 1991-08-26 | 1995-12-12 | Uop | Catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks |
| CN1597861A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Preparation process for suspension bed hydrogenating cracking catalyst for slag oil |
| CN1609174A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Prepn process of catalyst for residual oil hydrocracking in suspension bed |
-
2012
- 2012-04-21 CN CN201210117812.5A patent/CN102658142B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4116820A (en) * | 1977-06-29 | 1978-09-26 | Shell Oil Company | Process for demetallizing of heavy hydrocarbons |
| US5474977A (en) * | 1991-08-26 | 1995-12-12 | Uop | Catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks |
| CN1597861A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Preparation process for suspension bed hydrogenating cracking catalyst for slag oil |
| CN1609174A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Prepn process of catalyst for residual oil hydrocracking in suspension bed |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105648220A (en) * | 2016-02-03 | 2016-06-08 | 台州天天环保科技有限公司 | Technology for recycling vanadium from hydrogenation tail oil of suspended bed |
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