CN1074930A - One-step method for hydrocracking poor raw oil - Google Patents
One-step method for hydrocracking poor raw oil Download PDFInfo
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- CN1074930A CN1074930A CN 93101935 CN93101935A CN1074930A CN 1074930 A CN1074930 A CN 1074930A CN 93101935 CN93101935 CN 93101935 CN 93101935 A CN93101935 A CN 93101935A CN 1074930 A CN1074930 A CN 1074930A
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Abstract
A kind of one-step method for hydrocracking poor raw oil, it is included in hydrogen and exists down, and under hydrocracking condition, stock oil and active ingredient be W-Mo-Ni, help active ingredient is that Sn-F, carrier are SiO
2-Al
2O
3The multi-functional compound hydrocracking catalyst contact of-beta-molecular sieve is with production high-quality intermediate distillate fuel oil etc.
Description
The present invention relates to the method for hydrogen cracking of hydrocarbon ils, say with having more, the present invention relates to a period of hydrocracking method of inferior heavy oil, for example one of the mixing oil of Lie Zhi wax tailings, catalytic cycle oil and vacuum distillate section one-pass method for hydrogen cracking.IPCC10G45/00。
Inferior heavy oil a period of hydrocracking method of the present invention comprises, in the presence of hydrogen, under the condition of hydrocracking, stock oil and active ingredient be W-Wo-Ni, help active ingredient is that Sn-F, carrier are SlO2-AL
2O
3The multi-functional compound hydrocracking catalyst contact of-beta-molecular sieve is with production high-quality intermediate distillate fuel oil.
As everyone knows, the content of nitride is very high in a kind of wax tailings that obtains in the production of grand celebration refinery, and total nitrogen content is greater than 2000PPm.Make raw material with this wax tailings, in hydrogenation process, its nitride changes into NH
3, NH
3The acid sites of hydrogenation catalyst is poisoned, cause the very fast decline of catalyst activity, even make catalyzer lose industrial use value; In addition, contain more colloid (4-7%(heavy) in the wax tailings), coke powder and condensed-nuclei aromatics (about 30% (weight)), reaction takes place to pay in them in hydrocracking process, cause coking and quicken to generate coke, cause the temperature rise speed of catalyzer to be accelerated, shorten work-ing life, impels the too early inactivation of catalyzer, causes hydrocracking to be split and put shut-down.
Overcome inferior heavy oil, particularly wax tailings carries out hydrocracking with existing problem in the method for producing intermediate distillate fuel oil, just must provide a kind of fine multi-functional hydrocracking catalyst, and a kind of feasible hydrocracking method is provided.
At present, still there is not a kind of catalyzer can be applicable to the hydrocracking process of the mixing raw material of processing inferior heavy oil, particularly processing coked waxy oil, catalytic cycle oil, reduced pressure distillate wet goods for a long time both at home and abroad.Certainly, it is heavy more not adopt one section one-pass processing to contain wax tailings 50%() above or to contain catalytic cycle oil 50%(heavy) above mixing raw material oil
Hydrocracking catalyst and hydrocracking method.
Present domestic and international industrial hydrocracking production equipment, most of molecular sieve type hydrocracking catalyst that uses, when handling wax tailings, there are two than hang-up: the one, because the cracking activity of molecular sieve is stronger, its hydrogenation activity relatively a little less than, therefore cause certain difficulty with regard to the hydrogenation that makes impurity atoies such as organic nitrogen compound and colloid.The 2nd, because the duct of molecular sieve is generally smaller, the molecule that the condensed-nuclei aromatics equal diameter is bigger just is difficult to enter in the duct of molecular sieve, causes the saturated open loop of hydrogenation of this quasi-molecule to cause difficulty.Above-mentioned two problems has not only been brought the of poor quality of hydrogenated oil, and, make catalyst activity stability descend significantly, even cause rapid catalyst deactivation.
At present, generally adopt two sections serial hydrocracking technologies or one section recycle to extinction hydrocracking process technology in the world.The report that hydrocracking processing contains the wax tailings mixing raw material has, for example countries such as the U.S., Japan, the Soviet Union.The crow of sneaking into the maximum refinery of wax tailings and be the former Soviet Union sends out refinery, and wax tailings mixed volume is the highest also has only 30% for it, and the hydrocracking industrial installation that it adopts is two reactors or three reactors, pack into two kinds of catalyzer or multiple catalyzer.Technological process is: material carries out hydrofining earlier through the hydrofining section, removes N, O, and impurity atoies such as S, material enters the hydrocracking section then, carries out hydrocracking reaction, makes the macromole oil plant change into less molecule and isomer molecule etc.Then, have again through a hydrofining, with the deficiency of post-refining effect, make that reaction carries out fully, guarantee that quality product reach the required standards.
The U.S. unites oily company and adopts two sections recycle to extinction hydrocracking process to containing the mixing raw material oil of 5～10% wax tailings, be introduced into hydrofining reactor (have one or two reactor pack into catalyst for refining) and carry out the stock oil refining reaction, remove nitride, oxide compound and sulfide etc.Enter the reactor that hydrocracking catalyst is housed then, carry out hydrocracking reaction, reaction mass enters back refining reaction device (the back catalyst for refining of perhaps packing in the hydrocracking reactor bottom) again, carries out post-refining, so that quality product reaches quality standards.Have only short-term to produce and demarcate report, no long-term production data.
One of purpose of the present invention provides a kind of multi-functional compound hydrocracking catalyst; Two of purpose of the present invention provides a kind of method for hydrogen cracking of hydrocarbon ils inferior, i.e. one section one-pass method for hydrogen cracking.Use multi-functional compound hydrocracking catalyst of the present invention and method for hydrogen cracking can process hydrocarbon feed inferior, for example wax tailings, catalytic cycle oil, vacuum distillate, propane deasphalting wet goods.Catalyzer of the present invention has good anti-poisoning capability, big appearance charcoal ability, good activity and stability etc., thus can long period (more than a year) normal process inferior heavy hydrocarbon feed, produce the fine intermediate oil, for example-No. 35 diesel oil, aviation kerosene and petroleum naphtha etc.
Multi-functional compound hydrocracking catalyst of the present invention is that 1246 Hydrobon catalysts, 3762 hydrocracking catalysts and 3812 catalyzer produced with Fushun No.3 Petroleum Factory are raw material, select its two or three, through processing, compound formulated.The chemical constitution of 1246 Hydrobon catalysts is generally NiO(4～7%), MoO
3(13～18%), SiO
2(20～25%), Al
2O
3The chemical constitution of (48～58%) (weight), 3762 hydrocracking catalysts is generally NiO(6～13%), WO
3(18～24%), SnO
2(4～9%), F(5～11%), Al
2O
3(44～49%), beta-molecular sieve (1～3%) (weight); The chemical constitution of 3812 catalyzer is generally NiO(5-8%), WO
3(20-24%), SiO
2(13-15%), AI
2O
3(50-59%) (weight).Because catalyzer, industrial catalyzer lot number difference, each components contents changes slightly.
The preparation method of compound hydrocracking catalyst of the present invention is to select 1246 and 3762 catalyzer of identical particle size for use, with 34-38%(V) and mixed 62-66%(V) formulated.Used feedstock particle size is preferably right cylinder or the stripe shape of Φ (3-4) X4mm, and two kinds of former bulk densities of half are approaching more good more.
1246,3762 and 3,812 three kinds of catalyzer can be selected the particle of its identical size, the requirement by the chemical constitution of required finished product compound hydrocracking catalyst is hybridly prepared into compound hydrocracking catalyst of the present invention in the proper ratio.
The chemical constitution of compound hydrocracking catalyst of the present invention (weight %) is: WO
3: 14-20, preferably 17-19; MoO
3: 3-10, preferably 3-8; NiO:5-10; Best 6-9; SnO
2: 2-6, preferably 3-6; F:4-8, preferably 4-7; SiO
2: 12-18; Best 12-15; Al
2O
3: 45-55; β-molecular sieve: 1-3, preferably 1-2.The general physical properties of compound hydrocracking catalyst of the present invention is: bulk density 0.82-0.98g/ml; Specific surface area 182-300m2/g; Pore volume 0.34-0.44ml/g; Mean pore size 28.0-40.0 ° of A; Granularity Φ (3-4) X4mm.
Use compound hydrocracking catalyst of the present invention, adopt one section one-pass method for hydrogen cracking, can processing coked waxy oil or the mixing oil of the suitable proportion of catalytic cycle oil and vacuum distillate, can process the mixing oil of the suitable proportion of propane deasphalting residual oil and vacuum distillate, also can process the mixing oil of the suitable proportion of normal pressure third fractional oil and first vacuum side stream, produce diesel oil or products such as aviation kerosene and petroleum naphtha-No. 35.
The production equipment that method for hydrogen cracking of the present invention is used, only need to install a hydrocracking reactor, the compound hydrocracking catalyst of the present invention of packing in the reactor, under appropriate reaction conditions, can finish hydrofining and hydrocracking reaction simultaneously, produce needed intermediate distillate fuel oil product.
Use compound hydrocracking catalyst of the present invention and method for hydrogen cracking; processing contains the above mixing raw material of wax tailings 50% when oily; must adopt for example nitrogen protection of rare gas element to stock oil, quicken green coke with contacting of air, guarantee stable the producing of long period to reduce stock oil.
Use compound hydrocracking catalyst of the present invention and method for hydrogen cracking, when processing contains the mixing raw material oil of 50% wax tailings, contained-No. 35 diesel oil distillates can reach 48-54%(heavily in the generation oil), and energy running steady in a long-term, the temperature rise coefficient of its reactor is less than answering 0.04 ℃/day.When processing atmosphere 3rd side cut oil and first vacuum side stream mixing raw material, naphtha yield can reach 56-64%(Wt in the generation oil), industrial operation did not have obvious temperature rise in more than 150 day.These show all that compound hydrocracking catalyst of the present invention has good active stability and to the selectivity of lightweight oil.In addition, compound hydrocracking catalyst of the present invention can be used for the hydro-upgrading coker gas oil, and hydrofining is handled hydrocracking tail oil with the manufacture white oil etc.
Method for hydrogen cracking of the present invention comprises, in the presence of hydrogen, and selected stock oil and said multi-functional compound hydrocracking catalyst contact reacts under suitable hydrocracking process condition.Said hydrocracking condition is: temperature of reaction 380-420 ℃, and reaction pressure 13.0～15.0MPa, hydrogen to oil volume ratio 1300～1500: 1, liquid hourly space velocity 0.8-1.2hr
-1
The present invention is further described with the following examples now, but the present invention is not limited to this.
Embodiment 1
Preparation compound hydrocracking catalyst A
(heavy %) is NiO6% with the industrial chemical constitution of Fushun No.3 Petroleum Factory, WO
322%, F8%, SnO
28%, β-molecular sieve 1.5%, SiO
210% and AL
2O
344.5%3762 hydrocracking catalysts and chemical constitution are NiO5%, MoO
315%, SiO
224% and Al
2O
356% 1246 Hydrobon catalysts are pressed 66% and 34% mixed, are mixed with the compound hydrocracking catalyst of requirement, and this catalyzer is called catalyst A.The chemical constitution of catalyst A is (heavy %): NiO5.66%, WO
314.52%, MoO
35.1%, SnO
25.27%, F5.28%, SiO
214.76%, β-molecular sieve 1.0% and Al
2O
348.41%.
Embodiment 2
Preparation compound hydrocracking catalyst B
The chemical constitution that Fushun No.3 Petroleum Factory is produced is (heavy %) NiO 10%, WO
321%, F7%, SnO
26%, β-molecular sieve 2%, SiO
28%, reaches Al
2O
346.0% 3762 hydrocracking catalysts, chemical constitution is (heavy %) NiO6%, MoO
315%, SiO
222% and Al
2O
357% 1246 Hydrobon catalyst and chemical constitution (heavy %) are NiO8%, WO
322%, SiO
214% and Al
2O
356% 3812 hydrogenation catalysts are pressed 60%, 25% and 15% mixed, the compound hydrocracking catalyst of preparation requirement, and this catalyzer is called catalyst B, and its chemical constitution (heavy %) is NiO8.7%, MoO
33.75%, WO
315.9%, SnO
23.6%, β-molecular sieve 1.2%, SiO
212.4% and Al
2O
350.25, F4%.
Embodiment 3
Use the compound hydrocracking catalyst A of embodiment 1 preparation, each 50%(is heavy with grand celebration wax tailings and depressed heavy oil) mixing oil as raw material, on the small-sized hydroeracking unit of 100ml, reactor adopts conventional catalyst loading method, carries out the hydrocracking test.The condition of hydrocracking is: volume space velocity 1.0hr when hydrogen pressure 15.0Mpa, 400 ℃-420 ℃ of temperature, liquid
-1, hydrogen to oil volume ratio 1380: 1.Used raw material oil properties is listed in table 1.The test-results data are listed in table 2.Through more than 4800 hours service test, the result be the yield (yield of＜350 ℃ distillate) of hydrogenated oil greater than 74%, generating in the oil-No. 35 diesel yields, to reach 54%(heavy), it is heavy that naphtha yield reaches 20%().Its temperature rise coefficient is less than should be 0.04 ℃/day in the entire test.This evidence, catalyst A have good hydrogenation activity and stability.
Table 1 raw material oil properties
Character stock oil I stock oil II
Density (20 ℃ of Kg/M3) 869.1～889.9 840.6～832.0
Boiling range (℃) HK 238～342 204～210
50% 389～410 354～371
90% 440～465 402～411
Do 487～510 425～440
Condensation point (℃)+33～+ 38+26～+ 31
Carbon residue (%) 0.20～0.31 0.10～0.20
The content of wax (%) 25.4～28.7 28.5～34.1
Sulfur-bearing (%) 0.18～0.24 0.10
Total nitrogen (ppm) 1400～2,100 100～210
Colloid (%) 3.9～6.9 1.8～2.2
Group composition (%):
Alkane+naphthenic hydrocarbon 59.6～68.4 85.6～89.1
The above aromatic hydrocarbons 23.9 of two virtues～33.0 6.5～8.5
Total aromatic hydrocarbons 31.2～41.4 10.5～14.2
Annotate: the stock oil I is wax tailings and each 50%(body of depressed heavy oil) mixing oil.The stock oil II be atmosphere 3rd side cut oil with first vacuum side stream with 40%: the mixing oil 60%(body).
Embodiment 4
Use embodiment 3 used stock oil, catalyzer, test technology condition, test at 3 liters medium-sized hydrogenation unit.In addition, also use 50% wax tailings and 50%(body) the mixing raw material oil of vacuum distillate carried out same test.The test-results of two kinds of stock oils is very similar, the yield of hydrogenated oil, the result that product distributes, the product technician has repeated the small-sized hydropyrolysis experiment of 100ml of embodiment 3.Test-results is listed in table 3.
Sneak into 20% dewaxing heavy gas oil in ※-stock oil.
Embodiment 5
Adopt character to be similar to the wax tailings 50%(body of the stock oil I in the table 1) with second line of distillation wax oil 50%(body) mixing raw material oil, use catalyst A, be 14.6MPa at pressure, 386 ℃ of temperature, volume space velocity 1.02hr during liquid
-1, under 1380: 1 the condition of hydrogen to oil volume ratio, at 120,000 tons of enterprising line operates of industrial hydroeracking unit, the result of test: in the hydrogenated oil＜and the yield of 350 ℃ of distillates reaches 76%, and wherein-No. 35 diesel yield reaches 51%, naphtha yield 25%(is heavy).In addition, also the raw material II of listing in table 1 with character is tested, and just can reach above-mentioned level under 350 ℃ temperature.
Embodiment 6
Press the method for embodiment 1, system affair compound hydrocracking catalyst A45 ton is on the hydrocracking industrial installation that the annual working ability of the grand celebration refinery of packing into is 260,000 tons.Before going into operation catalyzer is given sulfuration.360 ℃ of working pressure 14.0MPa, temperature of reaction, volume space velocity 1.4hr when hydrogen oil volume 1500: 1, liquid
-1Condition under, oily II processes raw material.Liquid yield reaches 96.7% as a result, and＜350 ℃ distillate yield reaches 85%, and wherein naphtha yield 63%, and-No. 35 diesel yield 22%(is heavy).
Embodiment 7
Use the catalyst B of embodiment 2 preparations, adopt device and the processing condition of embodiment 3, processing 45% catalytic cycle oil and 55%(body) the mixing raw material of vacuum distillate, when 400 ℃ temperature of reaction, liquid yield reaches 97.5%, and＜350 ℃ distillate yield reaches 75%, generates-No. 35 diesel yields 55% in the oil, naphtha yield 20%, catalyzer temperature rise are 0.04 ℃/day.
The comparative example 1
Chemical constitution (weight) NiO2.0-4.0% that uses Fushun No.3 Petroleum Factory to produce, WO
325-35%, SiO
220-28%, all the other are Al
2O
3219 hydrocracking catalysts, on the device identical, carry out the initial activity test with identical stock oil and identical test conditions with embodiment 3, test-results is listed in table 4.
The comparative example 2
Use 3762 hydrocracking catalysts, carry out the test identical with comparative example 1, also carry out longevity test, the result of initial activity test also lists in table 4, and the longevity test reaction result lists in 5.
Claims (3)
1, a kind of inferior feedstock oil a period of hydrocracking processing method, it is included in hydrogen and exists down, and under hydrocracking condition, stock oil and active ingredient be W-Mo-Ni, help active ingredient is that Sn-F, carrier are SiO
2-Al
2O
3The multi-functional compound hydrocracking catalyst contact of-beta-molecular sieve, with production high-quality intermediate distillate fuel oil, the chemical constitution of said multi-functional compound hydrocracking catalyst (Wt%) is: WO
314-20, MoO
33-10, NiO 5-10, SnO
22-6, F 4-8, SiO
212-18, Al
2O
345-55, beta-molecular sieve 1-3; Said hydrocracking condition is: temperature of reaction 380-420 ℃, reaction pressure 13.0-15.0MPa, hydrogen to oil volume ratio 1300-1500: 1, volume space velocity 0.8-1.2hr during liquid
-1
2, according to a period of hydrocracking method of claim 1, wherein said stock oil is 50-70%.The mixing oil of the mixing oil of the mixing oil of wax tailings and 30-50% vacuum distillate, catalytic cycle oil and vacuum distillate, normal pressure third fractional oil and first vacuum side stream or the mixing oil of propane deasphalting residual oil and vacuum distillate.
3, want a period of hydrocracking method of right 1 or 2 according to right, wherein the chemical constitution of said multi-functional compound hydrocracking catalyst (Wt%) is: WO
317-19, MoO
33-8, NiO6-9, SnO
23-6, F4-7, beta-molecular sieve 1-2, SiO
212-15, all the other are Al
2O
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93101935 CN1028650C (en) | 1993-03-05 | 1993-03-05 | One-step method for hydrocracking poor raw oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93101935 CN1028650C (en) | 1993-03-05 | 1993-03-05 | One-step method for hydrocracking poor raw oil |
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| Publication Number | Publication Date |
|---|---|
| CN1074930A true CN1074930A (en) | 1993-08-04 |
| CN1028650C CN1028650C (en) | 1995-05-31 |
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ID=4983858
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93101935 Expired - Fee Related CN1028650C (en) | 1993-03-05 | 1993-03-05 | One-step method for hydrocracking poor raw oil |
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|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006111093A1 (en) * | 2005-04-21 | 2006-10-26 | China Petroleum & Chemical Corporation | A hydrogenation catalyst and its application |
| CN100381543C (en) * | 2004-10-29 | 2008-04-16 | 中国石油化工股份有限公司 | Hydrocracking method for composite catalyst bed layer |
| CN102154024A (en) * | 2011-02-21 | 2011-08-17 | 何巨堂 | Hydro-conversion integration method for high-nitrogen high-arene oil |
| US9534178B2 (en) | 2013-01-30 | 2017-01-03 | Petrochina Company Limited | Distillate two-phase hydrogenation reactor and hydrogenation method |
-
1993
- 1993-03-05 CN CN 93101935 patent/CN1028650C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381543C (en) * | 2004-10-29 | 2008-04-16 | 中国石油化工股份有限公司 | Hydrocracking method for composite catalyst bed layer |
| WO2006111093A1 (en) * | 2005-04-21 | 2006-10-26 | China Petroleum & Chemical Corporation | A hydrogenation catalyst and its application |
| EP2463025A1 (en) * | 2005-04-21 | 2012-06-13 | China Petroleum & Chemical Corporation | Ni/Mo/W supported hydrogenation catalyst containing P or F and process for hydrocarbon hydrogenation |
| US8697598B2 (en) | 2005-04-21 | 2014-04-15 | China Petroleum & Chemical Corporation | Hydrogenation catalyst and use thereof |
| CN102154024A (en) * | 2011-02-21 | 2011-08-17 | 何巨堂 | Hydro-conversion integration method for high-nitrogen high-arene oil |
| US9534178B2 (en) | 2013-01-30 | 2017-01-03 | Petrochina Company Limited | Distillate two-phase hydrogenation reactor and hydrogenation method |
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| Publication number | Publication date |
|---|---|
| CN1028650C (en) | 1995-05-31 |
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