CN102658142B - 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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- 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 24
- 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 14
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000001556 precipitation 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
- 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
- 239000000243 solution Substances 0.000 claims description 17
- 101710089042 Demethyl-4-deoxygadusol synthase Proteins 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 238000000944 Soxhlet extraction Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 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
- 238000011010 flushing procedure Methods 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
- 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
- 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
- 238000012545 processing Methods 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 7
- 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
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000010426 asphalt Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 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
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 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
- 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
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 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
- 238000005259 measurement Methods 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
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 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
- 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, is a kind of residual oil hydrocatalyst oolith stone and the method that obtains light oil and vanadium from Tahe residual oil.
Background technology
tahe residual oil has that lower H/C ratio, viscosity are large, sulphur and asphalt content is high, particularly content of vanadium high of tenor, belongs to a kind of poor residuum that is difficult to secondary operations.Because the existence of metallic element vanadium can cause catalyst poisoning, cause 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 is generally used for producing road asphalt, has caused the wasting of resources.
ren Zhendong etc. are in petroleum technology and application (2006,24(3): in hydrocracking one literary composition of the normal slag of Tahe of 202-205) delivering under oil-soluble molybdenum catalyst, disclose following content: adopt oil-soluble disperse type catalyzer research Tahe reduced crude hydrocracking reaction, at 430 ℃, hydrogen first pressing is 7.0 MPa, 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 academic nd Annual Meeting collection (2005 of the 9th National Chemical technique, 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 the light oil of≤350 ℃ is 31.6wt%.
the trace vanadium existing in oil causes its viscosity significantly to increase, and association has occurred for vfanadium compound and asphalt in oil, has formed asphalitine gummed ion.In the separation of vfanadium compound in the Tahe reduced crude that Zhou Aihui delivers in China Petroleum Univ. (East-China) 2011, purification and evaluation one literary composition, following content is disclosed: vanadium is in the three-dimensional structure of resin and asphalt, only have destruction three-dimensional structure, just can discharge micromolecular vfanadium compound.Therefore, adopt the common processing mode such as heating or stirring, can not be removed and reclaim.
the patent No. is US4, and 116,820 american documentation literature discloses following content: under high temperature (370～450 ℃), process residual oil with sour modified activated carbon, active carbon aperture is between 1～10 nm, and the vanadium in heavy oil removes more than 80%.Liu Zhangyong is in China University Of Petroleum Beijing. and 2010 residual oil of delivering react-adsorb demetalization and study and in a literary composition, disclose following content: adopt the sour modified kaolin of sour modification, nickel-loaded and load molybdenum to carry out HDM reaction to Liaohe River reduced crude and Tahe decompression residuum, studied the distribution of nickel, vanadium in product and had form.The patent No. is 2998578/23-04(1982.08.23) Russ P document following content is disclosed: use produce titanium-aluminium alloy containing aluminum oxide waste material, 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, at 20～35 ℃, and the part vanadium porphyrin complex in adsorbing and extracting crude oil, the dosage of adsorbent is 8～10%, and the recovery rate of vanadium porphyrin complex is 97.2～98%.
visible, Tahe residual hydrocracking Shortcomings, reactive hydrogen first pressing or reaction pressure are larger, and yield of light oil is not high.The content of this asphaltene in vacuum residues is 21.8%, and vanadium concentration is 307 grams/ton, and the vanadium apportionment ratio in asphalitine is 87.9%, processing refining difficulty.
Summary of the invention
the invention provides a kind of residual oil hydrocatalyst oolith stone and from Tahe residual oil, obtain the method for light oil and vanadium, overcome the deficiency of prior art, realized and from Tahe residual oil, obtained light oil and vanadium, and cost is low, the rate of recovery is high, thereby take full advantage 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 in the steps below:
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 are the oolith shape ore of 0.2～2 mm;
second step rinses: clean with distilled water flushing;
the 3rd step is dry: at 150 ± 10 ℃, dry 30 minutes to 60 minutes;
the 4th step calcining: calcine at 600 ± 10 ℃ 1 hour to 2 hours, 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 carrying out in the steps below:
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 are the oolith shape ore of 0.2～2 mm;
second step rinses: clean with distilled water flushing;
the 3rd step is dry: at 150 ± 10 ℃, dry 30 minutes to 60 minutes;
the 4th step calcining: calcine at 600 ± 10 ℃ 1 hour to 2 hours, obtain residual oil hydrocatalyst oolith stone.
three of technical scheme of the present invention obtains in the following manner: a kind of method that obtains light oil and vanadium from Tahe residual oil of utilizing above-mentioned residual oil hydrocatalyst oolith stone, and it carries out in the steps below:
first step catalytic hydrogenation thermal cracking: add the proportioning of residual oil hydrocatalyst oolith stone 1.0～2.0 g by every 50 g residual oil, will
residual oil join and stir in sealed reactor with residual oil hydrocatalyst oolith stone, to logical purity in still be
99.99%hydrogen exchange 3 times to 5 times, be then pressurized to 1.0 MPa to 6.0 MPa, 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 completion of the reaction, be cooled to room temperature, take out product;
second step product separates: the product that the above-mentioned first step is obtained, carry out Soxhlet extraction with n-hexane and toluene successively, and obtain respectively light oil, asphalitine, residue;
the 3rd step residue roasting takes off charcoal: the residue that second step is obtained roasting at 550 ± 10 ℃, makes vanadium metal change V into until be all converted into ashes
2
o
5
;
the 4th step alkali dissolution method leaching: with the appropriate NaOH NaOH aqueous solution that obtains soluble in water, add the ashes that above-mentioned the 3rd step obtains and make the V in ashes
2
o
5
all dissolve and filter and obtain filtrate;
the 5th step precipitation: the filtrate that the 4th step is 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 solution 0.1 mL～0.5 mL, leave standstill 1 day～2 days, occur white precipitate;
the 6th step is decomposed: the product that the 5th step is obtained carries out suction filtration, then drying precipitate roasting is obtained to orange-yellow Powdered V
2
o
5
.
three further optimization and/or selection to technique scheme below:
in above-mentioned the 4th step, appropriate NaOH is for making V
2
o
5
all dissolve and pH till between 8 to 9.
in above-mentioned the 4th step, the ashes of the 3rd step are progressively added in sodium hydroxide solution, boil 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 cake 3～5 times, then will be deposited at 105 ℃ and dry after 1 hour～2 hours, roasting 3 hours～5 hours at 475 ± 10 ℃ again, just obtains orange-yellow Powdered V
2
o
5
.
in above-mentioned second step, by the product of the first step, carry out Soxhlet extraction with n-hexane and toluene successively, extraction temperature is respectively 110 ℃ and 150 ℃, and the extracting time is 72 hours～and 96 hours; Wherein, n-hexane DDGS is defined as oil, and n-hexane insoluble matter toluene DDGS is asphalitine, and toluene insolubles is 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:
(1) Tahe residual oil catalytic pyrolysis processing, obtaining oily yield is 49.8～76.6%, and raw slag rate is 7.9～27.5%, and the apportionment ratio of vanadium in residue is 50.1～99.3%.
(2) be 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, oily yield is 61.29%, yield of light oil is 50.1%; Raw slag rate is 20.32%, and the apportionment ratio of vanadium in residue is 95.55%.
(3) adopt the V in the disposable leaching ashes of alkali dissolution method
2
o
5
, leaching rate >96wt%.The V obtaining with the roasting of precipitation ammonium metavanadate
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, and mild condition, step are simple, thereby cost is lower, and the rate of recovery is higher; Thereby be conducive to making full use of of Tahe residual oil resource.
The specific embodiment
the present invention is not subject to the restriction of following embodiment, can determine concrete embodiment according to the technical scheme of the invention described above and actual conditions.
below in conjunction with embodiment, the present invention is done to further discussion:
embodiment 1, this residual oil hydrocatalyst oolith stone obtains in the steps below:
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 are the oolith shape ore of 0.2～2 mm;
second step rinses: clean with distilled water flushing;
the 3rd step is dry: at 150 ± 10 ℃, dry 30 minutes to 60 minutes;
the 4th step calcining: calcine at 600 ± 10 ℃ 1 hour to 2 hours, obtain residual oil hydrocatalyst oolith stone.
embodiment 2, this residual oil hydrocatalyst oolith stone obtains in the steps below:
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 rinses: clean with distilled water flushing;
the 3rd step is dry: at 140 ℃ or 160 ℃, dry 30 minutes or 60 minutes;
the 4th step calcining: calcine at 590 ℃ or 610 ℃ 1 hour or 2 hours, obtain residual oil hydrocatalyst oolith stone.
embodiment 3, the method that should obtain light oil and vanadium from Tahe residual oil is carried out in the steps below:
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 every 50 g residual oil, will
residual oil join and stir in sealed reactor with residual oil hydrocatalyst oolith stone, to logical purity in still be
99.99%(percent by volume)hydrogen exchange 3 times to 5 times, be then pressurized to 1.0 MPa to 6.0 MPa, 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 completion of the reaction, be cooled to room temperature, take out product;
second step product separates: the product that the above-mentioned first step is obtained, carry out Soxhlet extraction with n-hexane and toluene successively, and obtain respectively light oil, asphalitine, residue;
the 3rd step residue roasting takes off charcoal: the residue that second step is obtained roasting at 550 ± 10 ℃, makes vanadium metal change V into until be all converted into ashes
2
o
5
;
the 4th step alkali dissolution method leaching: with the appropriate NaOH NaOH aqueous solution that obtains soluble in water, add the ashes that above-mentioned the 3rd step obtains and make the V in ashes
2
o
5
all dissolve and filter and obtain filtrate;
the 5th step precipitation: the filtrate that the 4th step is obtained maintains 30 ℃ to 50 ℃, to add mass percent concentration by every 5.0 g ashes components be 50%～60% ammonium chloride solution 7 mL～10 mL, splash into 50mg/L～150 mg/L ammonium metavanadate solution 0.1 mL～0.5 mL, leave standstill 1 day～2 days, occur white precipitate;
the 6th step is decomposed: the product that the 5th step is obtained carries out suction filtration, then drying precipitate roasting is obtained to orange-yellow Powdered V
2
o
5
.
embodiment 4, the method that should obtain light oil and vanadium from Tahe residual oil is carried out in the steps below:
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 and stir in sealed reactor with residual oil hydrocatalyst oolith stone, to logical purity in still be
99.99%(percent by volume)hydrogen exchange 3 times or 5 times, be then pressurized to 1.0 MPa or 6.0 MPa, 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 completion of the reaction, be cooled to room temperature, take out product;
second step product separates: the product that the above-mentioned first step is obtained, carry out Soxhlet extraction with n-hexane and toluene successively, and obtain respectively oil, asphalitine, residue;
the 3rd step residue roasting takes off charcoal: the residue that second step is obtained roasting at 540 ℃ or 560 ℃, makes vanadium metal change V into until be all converted into ashes
2
o
5
;
the 4th step alkali dissolution method leaching: with the appropriate NaOH NaOH aqueous solution that obtains soluble in water, add the ashes that above-mentioned the 3rd step obtains and make the V in ashes
2
o
5
all dissolve and filter and obtain filtrate;
the 5th step precipitation: the filtrate that the 4th step is obtained maintains 30 ℃ or 50 ℃, add mass percent concentration to be 50% or 60% ammonium chloride solution 7 mL or 10 mL, to splash into 50mg/L or 150 mg/L ammonium metavanadate solution 0.1 mL or 0.5 mL by every 5.0g ashes component, leave standstill 1 day or 2 days, separate out a large amount of white precipitates;
the 6th step is decomposed: the product that the 5th step is obtained carries out suction filtration, then drying precipitate roasting is obtained to orange-yellow Powdered V
2
o
5
.
embodiment 5, is with the difference of embodiment 3 and 4: in the 4th step of embodiment 5, appropriate NaOH is for making V
2
o
5
all dissolve and pH till between 8 to 9.
embodiment 6, is with the difference of embodiment 3 and 4: in the 4th step of embodiment 6, appropriate NaOH is for making V
2
o
5
all dissolve and pH 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 of the 3rd step are progressively added in sodium hydroxide solution, boil 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 of the 3rd step are progressively added in sodium hydroxide solution, boil 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, with mass percent concentration be 1～2% ammonium chloride solution 20～30 mL washing leaching cake 3～5 times, then will be deposited at 105 ℃ and dry after 1 hour～2 hours, roasting 3 hours～5 hours at 475 ± 10 ℃ again, just obtains orange-yellow Powdered V
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, with mass percent concentration be 1% or 2% ammonium chloride solution 20 mL or 30 mL washing leaching cakes 3 times or 5 times, then will be deposited at 105 ℃ and dry after 1 hour or 2 hours, roasting 3 hours or 5 hours at 465 ℃ or 485 ℃ again, just obtains orange-yellow Powdered V
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 the light oil of≤350 ℃ 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. raw slag rate, %=[m
residue
/ m
residual oil
] × 100%
5. yield of light oil, %=[m
light oil
/ m
residual oil
] × 100%
vanadium apportionment ratio calculates:
by the vanadium concentration in tannic acid-TGA spectrophotometry residual oil, oil and asphalitine.Vanadium concentration in residual oil is c
residual oil
, the vanadium concentration in oil is c
oil
, the vanadium concentration in asphalitine is c
asphalitine
.Calculate the vanadium apportionment ratio η in fuel-displaced, asphalitine and 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 above-described embodiment measurement and calculation is obtained to following result:
(1) Tahe residual oil catalytic pyrolysis processing, obtaining oily yield is 49.8～76.6%, and raw slag rate is 7.9～27.5%, and the apportionment ratio of vanadium in residue is 50.1～99.3%.
(2) be 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, oily yield is 61.29%, yield of light oil is 50.1%; Raw slag rate is 20.32%, and the apportionment ratio of vanadium in residue is 95.55%.
(3) adopt the V in the disposable leaching ashes of alkali dissolution method
2
o
5
, leaching rate >96wt%.The V obtaining with the roasting of precipitation ammonium metavanadate
2
o
5
purity is high.From residual oil, reclaim vanadium, overall recovery reaches 91.7wt%.
Claims (10)
1. a residual oil hydrocatalyst oolith stone, is characterized in that obtaining in the steps below:
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 are the oolith shape ore of 0.2～2 mm;
Second step rinses: clean with distilled water flushing;
The 3rd step is dry: at 150 ± 10 ℃, dry 30 minutes to 60 minutes;
The 4th step calcining: calcine at 600 ± 10 ℃ 1 hour to 2 hours, obtain residual oil hydrocatalyst oolith stone.
2. a production method for residual oil hydrocatalyst oolith stone, is characterized in that carrying out in the steps below:
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 rinses: clean with distilled water flushing;
The 3rd step is dry: at 150 ± 10 ℃, dry 30 minutes to 60 minutes;
The 4th step calcining: calcine at 600 ± 10 ℃ 1 hour to 2 hours, obtain residual oil hydrocatalyst oolith stone.
3. a method that obtains light oil and vanadium from Tahe residual oil of utilizing residual oil hydrocatalyst oolith stone described in claim 1, is characterized in that carrying out in the steps below:
First step catalytic hydrogenation thermal cracking: add the proportioning of residual oil hydrocatalyst oolith stone 1.0～2.0 g by every 50 g residual oil, will
residual oil join and stir in sealed reactor with residual oil hydrocatalyst oolith stone, to logical purity in still be
99.99%hydrogen exchange 3 times to 5 times, be then pressurized to 1.0 MPa to 6.0 MPa, 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 completion of the reaction, be cooled to room temperature, take out product;
Second step product separates: the product that the above-mentioned first step is obtained, carry out Soxhlet extraction with n-hexane and toluene successively, and obtain respectively oil, asphalitine, residue;
The 3rd step residue roasting takes off charcoal: the residue that second step is obtained roasting at 550 ± 10 ℃, makes vanadium metal change V into until be all converted into ashes
2o
5;
The 4th step alkali dissolution method leaching: with the appropriate NaOH NaOH aqueous solution that obtains soluble in water, add the ashes that above-mentioned the 3rd step obtains and make the V in ashes
2o
5all dissolve and filter and obtain filtrate;
The 5th step precipitation: the filtrate that the 4th step is 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 solution 0.1 mL～0.5 mL, leave standstill 1 day～2 days, occur white precipitate;
The 6th step is decomposed: the product that the 5th step is obtained carries out suction filtration, then drying precipitate roasting is obtained to orange-yellow Powdered V
2o
5.
4. the method that obtains light oil and vanadium from Tahe residual oil according to claim 3, is characterized in that in the 4th step, and appropriate NaOH is for making V
2o
5all dissolve and pH till between 8 to 9.
5. according to the method that obtains light oil and vanadium from Tahe residual oil described in claim 3 or 4, it is characterized in that, in the 4th step, the ashes of the 3rd step being progressively added in sodium hydroxide solution, boil 1 hour to 2 hours.
6. according to the method that obtains light oil and vanadium from Tahe residual oil described in claim 3 or 4, it is characterized in that in the 6th step, vacuum is 0.01～0.02 MPa, with mass percent concentration be 1～2% ammonium chloride solution 20～30 mL washing leaching cake 3～5 times, then will be deposited at 105 ℃ and dry after 1 hour～2 hours, roasting 3 hours～5 hours at 475 ± 10 ℃ again, just obtains orange-yellow Powdered V
2o
5.
7. the method that obtains light oil and vanadium from Tahe residual oil according to claim 5, it is characterized in that in the 6th step, vacuum is 0.01～0.02 MPa, with mass percent concentration be 1～2% ammonium chloride solution 20～30 mL washing leaching cake 3～5 times, then will be deposited at 105 ℃ and dry after 1 hour～2 hours, roasting 3 hours～5 hours at 475 ± 10 ℃ again, just obtains orange-yellow Powdered V
2o
5.
8. according to the method that obtains light oil and vanadium from Tahe residual oil described in claim 3 or 4, it is characterized in that in second step, by the product of the first step, carry out Soxhlet extraction with n-hexane and toluene respectively, extraction temperature is respectively 110 ℃ and 150 ℃, and the extracting time is 72 hours～and 96 hours; Wherein, n-hexane DDGS is defined as oil, and n-hexane insoluble matter toluene DDGS is asphalitine, and toluene insolubles is residue, and the n-hexane DDGS of boiling point≤350 ℃ is defined as light oil.
9. the method that obtains light oil and vanadium from Tahe residual oil according to claim 5, it is characterized in that in second step, by the product of the first step, carry out Soxhlet extraction with n-hexane and toluene successively, extraction temperature is respectively 110 ℃ and 150 ℃, and the extracting time is 72 hours～and 96 hours; Wherein, n-hexane DDGS is defined as oil, and n-hexane insoluble matter toluene DDGS is asphalitine, and toluene insolubles is residue, and the n-hexane DDGS of boiling point≤350 ℃ is defined as light oil.
10. the method that obtains light oil and vanadium from Tahe residual oil according to claim 7, it is characterized in that in second step, by the product of the first step, carry out Soxhlet extraction with n-hexane and toluene successively, extraction temperature is respectively 110 ℃ and 150 ℃, and the extracting time is 72 hours～and 96 hours; Wherein, n-hexane DDGS is defined as oil, and n-hexane insoluble matter toluene DDGS is asphalitine, and toluene insolubles is residue, and the n-hexane DDGS of boiling point≤350 ℃ is defined as light oil.
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|---|---|---|---|
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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 |
-
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 |
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