CN1233798C - Preparation process for suspension bed hydrogenating cracking catalyst for slag oil - Google Patents
Preparation process for suspension bed hydrogenating cracking catalyst for slag oil Download PDFInfo
- Publication number
- CN1233798C CN1233798C CN 03133996 CN03133996A CN1233798C CN 1233798 C CN1233798 C CN 1233798C CN 03133996 CN03133996 CN 03133996 CN 03133996 A CN03133996 A CN 03133996A CN 1233798 C CN1233798 C CN 1233798C
- Authority
- CN
- China
- Prior art keywords
- suspension bed
- oil
- temperature
- catalyst
- cracking catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention discloses a preparation process for a suspension bed hydrogenating cracking catalyst for slag oil, which makes mill tailings of molybdenum ore or ore dressing waste slag as raw materials, and the obtained solution can be used as the suspension bed hydrogenating cracking catalyst after the processing procedures, such as high temperature roasting, the leaching of chemical agents, etc. The catalyst can uniformly disperse in heavy oil or residual oil and can exist in hydrogen, and the inferior oil or the residual oil containing the catalyst is hydrocracked to be a light end product by the suspension bed. The suspension bed hydrogenating cracking catalyst prepared by the method of the present invention has the characteristics of low cost, good environment, high yield of the light end product, etc.
Description
Technical field
The present invention relates to a kind of dreg-oil suspension bed hydrogenation cracking Preparation of catalysts method, particularly cheap dreg-oil suspension bed hydrogenation cracking Preparation of catalysts method.
Background technology
, market heavy along with the continuous change of crude oil constantly increases and the environmental regulation increasingly stringent the light-weight fuel oil demand, and each refinery more and more pays close attention to residual oil lighting technology, and wherein suspension bed residual oil hydrogenation is one of important channel of heavy residual oil deep process technology.The catalyzer that suspension bed residual oil hydrogenation technology is used has nothing in common with each other, and pressed powder (as natural mineral matter, being loaded with the coal dust of metal etc.) is arranged, oil soluble organometallic compound, water-soluble cpds etc.And the solid powder th-1 catalyst granularity is big, and dispersion effect is bad in residual oil raw material, and consumption is many, and is active low, and exists tail oil to separate and the downstream unit obstructing problem.The oil soluble organo-metallic catalyst is poisonous usually, and the content of metal active constituent is low in the organometallic compound.And water soluble metal catalyst toxicological harmless effect, satisfied environmental requirement and solved reactive system because the wear problem that solid particulate brings, thereby the efficient cheap water-soluble catalyst of development and exploitation becomes one of major subjects of each research institution and refinery in the world.The main active component of water-soluble catalyst is generally metals such as Mo, Ni, W, Co and V, and at present, the type catalyzer all directly uses the technical grade pharmaceutical chemicals to be prepared from, and makes that the catalyzer cost is higher.As US 5,474,977 phospho-molybdic acid and molybdenum oxide or mixing such as 12-molybdenum silicic acid and sulfuration alum, after the dissolving, join in the raw material with toluene in container, after dehydration, piptonychia benzene, sulfuration, generate catalyzer under hydroconversion condition, carry out hydrogenation reaction simultaneously.The activity of the hydrogenation of this catalyzer and inhibition green coke is still lower, and at 20.0MPa, 420 ℃, coke yield is 0.6～0.9w% under the reaction conditions of 2h, 510 ℃ when the easy cracked Lloydminster of processing is oily
+The component transformation efficiency is 63～68%.In the method that above-mentioned patent is mentioned, complex technical process, and used the deleterious toluene of the person as reagent, directly use the higher technical grade pharmaceutical chemicals of price to prepare catalyzer simultaneously, once by not reclaiming, cost is very high for catalyzer.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of preparation method of cheap hydrocracking catalyst for suspension bed.
Dreg-oil suspension bed hydrogenation cracking Preparation of catalysts procedure of the present invention is: milltailings or the waste residue in the beneficiation wastewater settling bowl with molybdenum ore are raw material, at first carry out high-temperature roasting, leach with chemical reagent solution then and handle and filter, filtrate promptly can be used as the dreg-oil suspension bed hydrogenation cracking catalyzer, also can concentrate or add behind other material as the dreg-oil suspension bed hydrogenation cracking catalyzer.In aforesaid method, can also wash the insolubles after the filtration with water, the filtrate that obtains and washings are mixed to be concentrated into metal content be 4～10%, obtain the dreg-oil suspension bed hydrogenation cracking catalyzer.Wherein, the high-temperature roasting temperature is 500～700 ℃, and temperature range is preferably: 550～650.Roasting time is: 2～6h.The chemical reagent that uses can be in ammoniacal liquor, sodium hydroxide, the potassium hydroxide etc. one or more.The weight concentration of chemical reagent solution is 20～40%, and the weight ratio of solution and solid material is 2: 1～5: 1.Extraction temperature is 20～90 ℃, and extraction time is 1～6h.
Advantage of the present invention is:
1, the milltailings or the rejects of cheap catalyst employing molybdenum ore of the present invention are raw material, have both made full use of Mineral resources, greatly reduce the catalyzer cost again, and environmentally friendly.
2, cheap catalyst of the present invention also contains various active metals such as tungsten and nickel, iron, vanadium except that containing molybdenum, has synergy between the metal, and it is active high to make that catalyzer has, advantages such as good stability.Adopt catalyzer of the present invention, to the high inferior heavy of sulphur, nitrogen, metal impurities content height and carbon residue, when residual oil carries out floating bed hydrocracking, can obtain higher liquid yield, the green coke amount is lower simultaneously.
3, floating bed hydrogenation process catalyst levels is few, is generally≤300 μ g/g (in metal), can not reclaim, thereby has saved high catalyst recovery expense.
Embodiment
The hydrocracking catalyst for suspension bed of the inventive method preparation can be used for various heavy, dreg-oil suspension bed hydrogenation cracking processes, the organism that residual oil, heavy-gravity heavy crude oil, oil sands bitumen, shale oil and the dry distillation of coal that obtains as crude distillation obtains etc.
The consumption of the hydrocracking catalyst for suspension bed of the inventive method preparation is counted 50～1000 μ g/g with metal.Common floating bed hydrocracking reactor operating condition is: pressure 2～20MPa is preferably 8～14MPa; 400～470 ℃ of temperature are preferably 430～440 ℃; Liquid hourly space velocity 0.2～2.0h
-1, be preferably 0.7～2.0h
-1Hydrogen to oil volume ratio (under the standard pressure) 200～1200 is preferably 500～1000.
Further specify the solution of the present invention and effect below in conjunction with embodiment.
Embodiment 1
100 gram molybdenum ore beneficiation wastewater settling bowl waste residues are put into crucible (contain molybdenum 8.1% by analysis, tungsten 5.7%, nickel 1.2%, iron 4.7%), roasting is 4 hours in 650 ℃ retort furnace, taking out 50 gram calcining matters then is the three-necked bottle that 20% NaOH puts into 500ml with 100 gram concentration, three-necked bottle put into 60 ℃ water bath with thermostatic control isothermal reaction 2 hours, after reaction finishes, with cloth formula funnel suction filtration, wash insolubles then with water, filtrate and washing lotion are mixed put into beaker and evaporate portion water, obtain total metal concentration and be 8.4% concentrated solution, code name is C-1.
Embodiment 2
100 gram molybdenum ore milltailings are put into crucible (contain molybdenum 0.23% by analysis, tungsten 7.5%, nickel 0.7%, iron 6.8%), roasting is 4 hours in 550 ℃ retort furnace, taking out 50 gram calcining matters then is the three-necked bottle that 20% sodium hydroxide is put into 500ml with 100 gram concentration, three-necked bottle put into 80 ℃ water bath with thermostatic control isothermal reaction 4 hours, after reaction finishes, with cloth formula funnel suction filtration, wash insolubles then with water, filtrate and washing lotion are mixed put into beaker and evaporate portion water, obtain total metal concentration and be 5.2% concentrated solution, code name is C-2.
Embodiment 3
100 gram molybdenum ore beneficiation wastewater settling bowl waste residues are put into crucible (contain molybdenum 8.1% by analysis, tungsten 5.7%, nickel 1.2%, iron 4.7%), roasting is 6 hours in 600 ℃ retort furnace, taking out 50 gram calcining matters then is the three-necked bottle that 25% ammoniacal liquor is put into 500ml with 200 gram concentration, three-necked bottle put into 35 ℃ water bath with thermostatic control isothermal reaction 6 hours, after reaction finishes, with cloth formula funnel suction filtration, wash insolubles then with water, filtrate and washing lotion are mixed put into beaker and evaporate portion water, obtain total metal concentration and be 6.5% concentrated solution, code name is C-3.
Embodiment 4
100 gram molybdenum ore milltailings are put into crucible (contain molybdenum 0.23% by analysis, tungsten 7.5%, nickel 0.7%, iron 6.8%), roasting is 2 hours in 500 ℃ retort furnace, the calcining matters that take out 50 grams then are the three-necked bottle that 40% NaOH puts into 500ml with 150 gram concentration, three-necked bottle put into 90 ℃ water bath with thermostatic control isothermal reaction 2 hours, after reaction finishes, with cloth formula funnel suction filtration, wash insolubles then with water, filtrate and washing lotion are mixed put into beaker and evaporate portion water, obtain total metal concentration and be 7.8% concentrated solution, code name is C-4.
Embodiment 5～8
Example 5～8 test raw materials are isolated island residual oil, and test raw material character sees Table 1.This residual oil sulphur content height as shown in Table 1, metal content is higher, and colloid, asphalt content are also higher, and carbon residue reaches 8.73w%, is a kind of more unmanageable poor residuum.Example 5～8 is being investigated on the autoclave under operational conditions such as different pressures, temperature, reaction times, catalyzer add-on, the conversion of residual oil and the coke forming property of reaction process when using the different catalyzer of forming, and test-results is listed in the table 2.Show that by the listed result of table 2 cheap water-soluble catalyst of the present invention has active high advantage.Adopt catalyzer of the present invention, to the high inferior heavy of sulphur, nitrogen, metal impurities content height and carbon residue, when residual oil carries out floating bed hydrocracking, can suppress green coke to greatest extent, under add-on≤300 μ g/g (in metal) conditions,＜500 ℃ of liquid product yields can reach more than the 70m%.
Table 1 stock oil character
The normal slag of project isolated island
Density kg/m
3(20 ℃) 965.3
Carbon residue w% 8.73
Ultimate analysis w%
C 84.78
H 11.61
S 1.94
N 0.1316
Metal analysis μ g/g
Fe 12.47
Ni 24.47
V 4.91
Ca 14.92
Cu 0.03
Na 26.53
Proximate analysis w%
Saturated branch 31.4
Fragrance divides 30.6
Colloid 36.6
Bituminous matter 1.6
Table 2 autoclave test result
Experiment numbers 5678
Project C-1 C-2 C-3 C-4
Catalytic amount, μ g/g 300 250 250 300
Reaction pressure, MPa 9 14 10 8
Temperature of reaction, ℃ 435 438 430 432
In the reaction times, min 60 45 45 60
＞500 ℃ of tail oil yields, w% 20.1 19.0 26.1 22.1
Coke, w% 0.7 1.0 0.3 0.5
Claims (4)
1, a kind of dreg-oil suspension bed hydrogenation cracking Preparation of catalysts method, it is characterized in that milltailings or the waste residue in the beneficiation wastewater settling bowl with molybdenum ore are raw material, at first carry out high-temperature roasting, leach with chemical reagent solution then and handle and filter, filtrate is as the dreg-oil suspension bed hydrogenation cracking catalyzer;
Wherein said high-temperature roasting temperature is 500～700 ℃, and roasting time is 2～6h; Described chemical reagent is one or more in ammoniacal liquor, sodium hydroxide, the potassium hydroxide; The weight ratio of described chemical reagent solution and solid material is 2: 1～5: 1, and extraction temperature is 20～90 ℃, and extraction time is 1～6h.
2, in accordance with the method for claim 1, it is characterized in that washing with water the filtration insolubles, with the washings that obtains with filtrate mixing to be concentrated into metal content be 4～10%, as the dreg-oil suspension bed hydrogenation cracking catalyzer.
3, in accordance with the method for claim 1, it is characterized in that described high-temperature roasting temperature is 550～650 ℃.
4, in accordance with the method for claim 1, the weight concentration that it is characterized in that described chemical reagent solution is 20～40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03133996 CN1233798C (en) | 2003-09-15 | 2003-09-15 | Preparation process for suspension bed hydrogenating cracking catalyst for slag oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03133996 CN1233798C (en) | 2003-09-15 | 2003-09-15 | Preparation process for suspension bed hydrogenating cracking catalyst for slag oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597861A CN1597861A (en) | 2005-03-23 |
| CN1233798C true CN1233798C (en) | 2005-12-28 |
Family
ID=34658941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03133996 Expired - Lifetime CN1233798C (en) | 2003-09-15 | 2003-09-15 | Preparation process for suspension bed hydrogenating cracking catalyst for slag oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1233798C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658142B (en) * | 2012-04-21 | 2014-06-25 | 新疆大学 | Residual oil hydrogenation catalyst oolitic stones and method for obtaining light oil and vanadium from Tahe residue oil |
| KR102385590B1 (en) | 2014-07-17 | 2022-04-11 | 사빅 글로벌 테크놀러지스 비.브이. | Upgrading hydrogen deficient streams using hydrogen donor streams in a hydropyrolysis process |
| CN106140184A (en) * | 2016-06-27 | 2016-11-23 | 北京华福工程有限公司 | The preparation method of a kind of heavy oil floating bed hydrocracking catalyst and gained serosity thereof |
| CN106140185A (en) * | 2016-06-27 | 2016-11-23 | 北京华福工程有限公司 | Useless hydrogenation catalyst prepares method and the gained serosity thereof of suspension bed hydrogenation catalyst |
| CN110465295B (en) * | 2018-05-10 | 2022-04-19 | 李大鹏 | Suspension bed hydrogenation multi-element composite iron-based catalyst and preparation method thereof |
-
2003
- 2003-09-15 CN CN 03133996 patent/CN1233798C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1597861A (en) | 2005-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101927167B (en) | Compound coal tar hydrogenation catalyst and preparation method thereof | |
| CN1078487A (en) | Integrated processes to heavy still bottoms pre-treatment and hydrocracking | |
| CN101041789A (en) | Waste lubricating oil hydrogenation reproducing method | |
| WO2014183429A1 (en) | Heterogeneous suspension-bed hydrogenation method for coal-based oil product | |
| CN102895973B (en) | Complex catalyst for direct liquefaction of coal, and preparation method thereof | |
| CA1153720A (en) | Upgrading of hydrocarbon feedstock | |
| CA1157409A (en) | Desulfurization, demetalation and denitrogenation of coal | |
| CN1233798C (en) | Preparation process for suspension bed hydrogenating cracking catalyst for slag oil | |
| CN1132910C (en) | Hydrocracking catalyst and process in suspension bed | |
| CN111876189B (en) | Method for two-stage catalytic direct liquefaction of coal and application thereof | |
| CN1145685C (en) | Process for coal liquefaction | |
| CN1243082C (en) | Prepn process of catalyst for residual oil hydrocracking in suspension bed | |
| CA1322746C (en) | Hydrocracking of heavy oils in presence of petroleum coke derived from heavy oil coking operations | |
| CN115888812A (en) | Hydrotreating oil-soluble bimetallic catalyst and preparation method thereof | |
| CN103059915A (en) | Poor-quality heavy oil hydro-upgrading method | |
| JPS6126836B2 (en) | ||
| CN115532309B (en) | Preparation method and application of oil-soluble catalyst for slurry bed hydrogenation | |
| CN114427038B (en) | Method for recycling metal components in tail oil | |
| CN1227337C (en) | Catalyst for hydrogenation upgrading heavy and residual oil and application thereof | |
| CN1133727C (en) | Hydrocracking catalyst for oil-soluble suspension bed and its prepn | |
| CN1107712C (en) | Hydrocracking catalyst for suspension bed and its prepn | |
| CN116554925B (en) | Waste plastic pyrolysis oil hydrogenation purification method | |
| CN116496812B (en) | Waste plastic pyrolysis oil hydrogenation pretreatment method | |
| CN115475622B (en) | Preparation method and application of slurry bed hydrogenation catalyst based on waste porcelain powder carrier | |
| CN105727977B (en) | A kind of synthesis gas methanation substitutes the method for preparing catalyst of natural gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20051228 |
|
| CX01 | Expiry of patent term |