CN1362489A - Hydrocracking catalyst and process in suspension bed - Google Patents
Hydrocracking catalyst and process in suspension bed Download PDFInfo
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- CN1362489A CN1362489A CN 01106048 CN01106048A CN1362489A CN 1362489 A CN1362489 A CN 1362489A CN 01106048 CN01106048 CN 01106048 CN 01106048 A CN01106048 A CN 01106048A CN 1362489 A CN1362489 A CN 1362489A
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Abstract
The catalyst is one organic metal chelated formed from metals of families of VIII, VIB, VB and VIIB. Said catalyst can be uniformly dissolved in the heavy and residual oil, and in the presence of hydrogen gas the poor heavy and residual oil containing said catalyst can be passed through the suspended bed and hydrogenated and cracked into light product. Said ivnention is aimed at reducing catalyst cost, raising yield rate of heavy and residual oil suspended bed hydrogenation cracking light product, and reducing coking rate.
Description
The present invention relates to a kind of heavy, residual hydrocracking catalyzer and technology, particularly heavy, dreg-oil suspension bed hydrogenation cracking catalyzer and technology.
, market heavy along with the continuous change of crude oil extraction constantly increases the light-weight fuel oil demand and the raising day by day of environmental requirement, each refinery more and more pays close attention to residual oil lighting technology, wherein suspension bed residual oil hydrogenation is one of important approach, so each major oil companies competitively researchs and develops the hydrogenation of residual oil suspended bed technology.The catalyzer that is used for suspension bed residual oil hydrogenation technology mainly contains three kinds, is respectively: solid powder th-1 catalyst, water-soluble catalyst, oil-soluble catalyst.And the oil soluble metal catalyzer has not only satisfied environmental requirement but also solved the wear problem that reactive system brings owing to solid particulate, and is uniformly dispersed in weight, residual oil raw material, need not to add emulsifying agent.Thereby developing and develop oil-soluble catalyst efficiently becomes one of major subjects of each research institution and refinery in the world.
Adopt Fe (CO) in the United States Patent (USP) 5578197
5With the 2 ethyl hexanoic acid molybdenum be catalyzer, to contain 60m%504 ℃
+The Athabasca residual oil of hydrocarbon ils is raw material, catalyst metal add-on 5000 μ g/g, and add thinner in 2: 1 ratio.On autoclave, test 430 ℃ of temperature of reaction, reaction pressure 10MPa, reaction times 105min, 504 ℃
+Liquid yield be 27.0m%, coke is 3.8m%; United States Patent (USP) 4579838 is used CrO
3With the alcohol reaction, get oil soluble di-t-butyl chromate, it is mixed with part heavy oil, containing H then
2There is heated mixt down in S gas, obtains catalyzer.Heating condition is 370～427 ℃, 0.7～14MPa, and chromium content is at 0.1～2m% in the gained slurry catalyst.This catalyzer is used for the floating bed hydrogenation that heavy Arab subtracts slag, at 14.4MPa, 443 ℃ of reactions down, when the catalyst metal add-on is 350 μ g/g, 524 ℃
+Transformation efficiency is 84.6m%, and coking yield is 1.43m%.
In the method that above-mentioned patent is mentioned, still there are some shortcomings, as: the Preparation of Catalyst more complicated, catalyzer (in metal) add-on is very big, is up to 5000 μ g/g, and this significantly increases the catalyzer cost, and coking yield reaches 1.43m% also than higher.
The purpose of this invention is to provide a kind of transformation efficiency height, highly selective and stable hydrocracking catalyst for oil-soluble suspension bed that coking yield is low, another object of the present invention provides that a kind of catalyzer add-on is low, the processing inferior heavy that can stablize long-term operation, the floating bed hydrocracking technology of residual oil.
Hydrocracking catalyst for suspension bed of the present invention is the transition metal organic chelate, and wherein metal content is 1～40 weight %, is preferably 5～20 weight %.
Described transition metal is selected from VIII, VB, VIB and VIIB family metallic compound, is preferably metallic elements such as Fe, Co, Ni, V, MnCr, Mo, W.Relatively the metallic compound of Shi Heing is: iron compound (better being iron(ic) chloride, iron nitrate), nickel compound (better being nickelous chloride, nickelous nitrate or single nickel salt), cobalt compounds (better being cobalt chloride, rose vitriol), vanadium compounds (better being vanadium fluoride, ammonium vanadate), manganese compound (better being Manganous chloride tetrahydrate, manganous sulfate), chromium compounds (better being chromium carbonate, basic chromic carbonate or chromium chloride), molybdenum thing (better being ammonium molybdate, molybdenum chloride), tungsten thing (better being ammonium tungstate, tungsten chloride).
Organic sequestering agent comprises that ketone, phenols, aldehydes, ethers, carboxylic acid, ester class, acyl class, oximes, amine, quinones, azo class, sulphur hydrazone and other contain the compound that organism such as hydroxyl, nitro, nitroso-group, carbonyl, thiocarbonyl group form.Wherein the sequestrant that relatively is fit to is: methyl ethyl diketone, benzoyl acetone, dimethylglyoxime, salicylic aldehyde, 18-is preced with-6 ethers, dibenzo-24-hat-8-ether, diethyldithiocar bamic acid (DDTC), thiooxine, disodium salt (EDTA), methyl aceto acetate, N-nitroso-group β-phenylhydroxylamine amine (cupferron), quadrol, protoporphyrin, dipyridyl, ferrosin, the diphenyl sulfide hydrazone, citric acid, sulfosalicylic acid, eriochrome black T, chrome black A, the 4-[2-pyridylazo]-Resorcinol (PAR) and 1-[2-pyridylazo]-in the beta naphthal (PAN) one or more.
Catalyzer of the present invention can be that each metal component reacts with organic sequestering agent respectively, also can severally mix and one or more organic sequestering agents reactions.
Preparation of catalysts method of the present invention is: VIII, VB, VIB and VIIB family metallic compound and organic sequestering agent are reacted, obtain organic metal chelate complex.
Suspension bed hydrocracking method of the present invention is:
With organic metal chelate complex hydrocracking catalyst for suspension bed of the present invention, with ordinary method, uniform dissolution is in weight, residual oil raw material; In the presence of hydrogen, make mixed raw materials oil under the floating bed hydrocracking condition, carry out hydrocracking.
The weight that the present invention relates to, residual oil can be the residual oils that crude distillation obtains, heavy-gravity heavy crude oil, the also organism that obtains of oil sands bitumen, shale oil and the dry distillation of coal.For different material oil, operational condition is different, and usually the floating bed hydrocracking reactor operating condition is: pressure 2～20MPa (be preferably 8～14Mpa), temperature 400～470 ℃ of (being preferably 430～450 ℃), liquid hourly space velocity 0.2～2.0h
-1(be preferably 0.7～1.5h
-1), hydrogen to oil volume ratio (under the standard pressure) 200～2000 (being preferably 500～1000), catalyst levels is counted 50～5000 μ g/g with weight metal, is preferably 200～400 μ g/g.
Advantage of the present invention is:
1, to have an oil soluble good for catalyzer of the present invention, and add-on is few, can≤300 μ g/g (in metal), active high, advantages such as good stability.Adopt oil soluble metal 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, and liquid product yield is improved more than the 5m%.
2, the oil-soluble catalyst that adopts in the floating bed hydrogenation process has suppressed the green coke of process effectively, thereby makes and do not contain solid particulate substantially in the tail oil.
3, the floating bed hydrogenation process is used very a spot of oil-soluble catalyst, can not reclaim catalyzer and save high catalyst recovery expense.
4, in the hydrocracking process of suspended bed of weight, residual oil, oil-soluble catalyst of the present invention can directly be dispersed in the oil, need not to add emulsifying agent, and the technology that simplifies the operation reduces running cost.
For further specifying all main points of the present invention, enumerate following examples.
Example 1
Place beaker to add 50 ml waters in load weighted 10.5 gram iron(ic) chloride and make its dissolving, in solution, add 25.1 gram methyl ethyl diketones, constantly stir, keeping pH value in the reaction process is 1, after reaction finishes, isolate water with separating funnel, residual solution 100 ℃ of air dryings 20 hours, is obtained product 28.4 grams at last, and it is mainly ferric acetyl acetonade, iron level is 15.8%, and code name is C-1.
Example 2
Place beaker to add 50 ml waters load weighted 12.3 gram cobalt chloride and make its dissolving, add 32.6 gram DDTC in solution, constantly stir, keeping pH value in the reaction process is 1, after reaction finishes, go out precipitation with filter paper filtering, water repetitive scrubbing 3 times will be deposited in then in 120 ℃ of air and carry out drying, obtain product 31.9 grams at last, it is mainly cobalt diethyldithiocarbamate, and cobalt contents is 16.2%, and code name is C-2.
Example 3
Placing beaker to add 50 ml waters load weighted 8.7 gram nickelous chlorides makes its dissolving, this solution is heated to 70 ℃, add 300 milliliter 10% dimethylglyoxime ethanolic soln in solution, drip less ammonia, constantly stir, after reaction finishes, go out precipitation with filter paper filtering, to precipitate the water repetitive scrubbing 3 times, 120 ℃ of air dryings 15 hours, obtain solid product 18.7 grams at last then, it is mainly dimethylglyoxime nickel, nickel content is 20.0%, and code name is C-3.
Example 4
Placing beaker to add 50 ml waters load weighted 8.0 gram chromium chlorides makes its dissolving, this solution is heated to 50 ℃, add 400 milliliter of 10% dimethylglyoxime ethanolic soln in solution, pH value remains on about 2 in the reaction process, constantly stir, after reaction finishes, go out precipitation with filter paper filtering, to precipitate the water repetitive scrubbing 3 times, 120 ℃ of air dryings 20 hours, obtain solid product 18.15 grams at last then, it is mainly dimethylglyoxime chromium, chromium content is 13.0%, and code name is C-4.
Example 5
Place beaker to add 50 ml waters load weighted 15.6 gram Manganous chloride tetrahydrates and make its dissolving, in solution, add 40.2 gram diethyldithiocar bamic acid solution, constantly stir, pH value remains on about 5 in the reaction process, after reaction finishes, go out precipitation with filter paper filtering, to precipitate the water repetitive scrubbing 3 times, to be deposited in then in 100 ℃ of air and carry out drying 25 hours, obtain solid product 40.57 grams at last, it is mainly diethyldithiocar bamic acid manganese, and manganese content is 15.5%, and code name is C-5.
Example 6
Place beaker to add 50 ml waters load weighted 5.6 gram molybdenum chlorides and make its dissolving, the mixed solution that in solution, adds 20 gram thiooxines and 300 milliliters of trichloromethanes, constantly stir, keeping pH value in the reaction process is 1, after reaction finishes, isolate water with separating funnel, residual solution 100 ℃ of air dryings 28 hours, is obtained product 15.7 grams at last, and it is mainly the thiooxine molybdenum, molybdenum content is 8.6%, and code name is C-6.
Example 7
Place beaker to add 50 ml waters load weighted 6.6 gram tungsten chlorides and make its dissolving, in solution, add the mixed solution of 20 gram thiooxines and 300 milliliters of trichloromethanes, and add 20 milliliters of EDTA solution, constantly stir, keeping pH value in the reaction process is 3, after reaction finishes, isolate water with separating funnel, with residual solution 100 ℃ of air dryings 26 hours, obtain product 14.5 grams at last, it is mainly thiooxine tungsten, and W content is 16.1%, and code name is C-7.
Example 8
Place beaker to add 50 ml waters load weighted 7.9 gram vanadium fluorides and make its dissolving, the mixed solution that in solution, adds 45 gram cupferrons and 500 milliliters of trichloromethanes, constantly stir, keeping pH value in the reaction process is 2, after reaction finishes, isolate water with separating funnel, residual solution 100 ℃ of air dryings 32 hours, is obtained product 42.2 grams at last, and it is mainly N-nitroso-group β-phenylhydroxylamine amine vanadium, content of vanadium is 6.0%, and code name is C-8.
Example 9
Place beaker adding 100 ml waters to make its dissolving load weighted 25.6 gram chromium chlorides and 16.1 gram nickelous chlorides, this solution is heated to 70 ℃, in solution, add 25 gram dimethylglyoxime and 300 milliliters of alcoholic acid mixing solutionss, constantly stir, after reaction finishes, go out precipitation with filter paper filtering, in residual solution, drip less ammonia then, till not producing precipitation, with filter paper filtering go out precipitation with twice be deposited in 120 ℃ of air dryings 30 hours, obtain solid product 21.1 grams at last, it is mainly dimethylglyoxime chromium and dimethylglyoxime nickel, metal content is 16.6%, and code name is C-9.
Example 10
Place beaker adding 100 ml waters to make its dissolving load weighted 4.5 gram tungsten chlorides and 5.5 gram molybdenum chlorides, the mixed solution that in solution, adds 30.0 gram thiooxines and 500 milliliters of trichloromethanes, and add 50 milliliters of EDTA solution, constantly stir, keeping pH value in the reaction process is 3, after reaction finishes, isolate water with separating funnel, with residual solution 100 ℃ of air dryings 36 hours, obtain product 28.2 grams at last, it is mainly thiooxine tungsten and thiooxine molybdenum, and metal content is 11.7%, and code name is C-10.
Example 11
C-1～C-8 catalyst by proportion is mixed, obtain containing the catalyzer of iron, cobalt, nickel, vanadium, manganese, chromium, molybdenum and tungsten, metal content is 12.7%, and the weight ratio of its iron, cobalt, nickel, vanadium, manganese, chromium, molybdenum and tungsten is: 1: 4: 3: 2: 1: 9: 1: 1, code name was C-11.
Embodiment 12～22
Example 12～22 test raw materials are husky light normal slag, and test raw material character sees Table 1.The saturated branch of this residual oil divides content higher with fragrance as shown in Table 1, and colloid is less, and bituminous matter is higher, and metal content is higher, and sulphur content is also higher, reaches 3.38m%, is a kind of more unmanageable poor residuum.Example 12～22 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 oil-soluble catalyst of the present invention has active high advantage.Adopt oil soluble metal 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 75m%.
Embodiment 23～29
Embodiment 23～29 is the comparison test that oil-soluble catalyst of the present invention and typical catalyst M carry out, and M is water-soluble Mo, Ni catalyzer, metal content 9.2m%.Test raw material is a vacuum residuum in the sand, and vacuum residuum feed character sees Table 3 in the sand.This residual oil sulphur, nitrogen content height as shown in Table 3, metal content is also higher, and asphalt content reaches 8.4m%, and carbon residue reaches 20.73m%, is a kind of more unmanageable poor residuum.Example 23～29 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 4.Can find out that by table 4 result oil-soluble catalyst of the present invention all is better than typical catalyst M at aspects such as＜500 ℃ of liquid yields and coking yields.
Embodiment 30～34
Example 30～34 test raw materials are the normal slag of isolated island, and test raw material character sees Table 5.This residual oil sulphur content height as shown in Table 5, metal content is higher, and colloid, asphalt content are also higher, and carbon residue reaches 8.73m%, is a kind of more unmanageable poor residuum.Example 30～34 is being investigated on the continuous hydrogenation device under operational conditions such as differential responses pressure, temperature of reaction, air speed and hydrogen-oil ratio, 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 6.Show that by the listed result of table 6 oil-soluble catalyst of the present invention has active high advantage.Adopt oil soluble metal 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 80m%.
The husky light normal slag feedstock property of table 1
| Project | Husky light normal slag |
| Density kg/m 3(20℃) | ????969.4 |
| Carbon residue m% | ????9.71 |
| Ultimate analysis m% | |
| ?????????C | ????84.76 |
| ?????????H | ????11.38 |
| ?????????S | ????3.38 |
| ?????????N | ????0.1694 |
| Metal analysis m% | |
| ?????????Fe | ????2.37 |
| ?????????Ni | ????11.10 |
| ?????????V | ????37.5 |
| ?????????Ca | ????1.25 |
| ?????????Cu | ????0.06 |
| ?????????Na | ????1.53 |
| Proximate analysis m% | |
| Saturated branch | ????40.3 |
| Fragrance divides | ????42.2 |
| Colloid | ????14.3 |
| Bituminous matter | ????3.2 |
The husky light normal slag autoclave test result of table 2
| Project | ??C-1 | ??C-2 | ??C-3 | ??C-4 | ??C-5 | ??C-6 | ??C-7 | ??C-8 | ??C-9 | ??C-10 | ??C-11 |
| Metal content m% | ??15.8 | ??16.2 | ??20.0 | ??13.0 | ??15.5 | ??8.6 | ??16.1 | ??6.0 | ??16.6 | ??11.7 | ??12.7 |
| Temperature of reaction ℃ | ??435 | ??434 | ??435 | ??437 | ??440 | ??445 | ??438 | ??440 | ??440 | ??439 | ??439 |
| Reaction pressure MPa | ??10 | ??8 | ??10 | ??12 | ??10 | ??10 | ??12 | ??10 | ??10 | ??10 | ??10 |
| Reaction times min | ??30 | ??60 | ??45 | ??60 | ??30 | ??30 | ??30 | ??30 | ??60 | ??30 | ??30 |
| Catalytic amount μ g/g | ??300 | ??300 | ??300 | ??250 | ??300 | ??250 | ??250 | ??300 | ??250 | ??300 | ??300 |
| Product distribution m% | |||||||||||
| ????＜180℃ | ??9.6 | ??12.3 | ??12.5 | ??14.4 | ??9.2 | ??13.6 | ??11.7 | ??9.5 | ??15.7 | ??13.9 | ??15.5 |
| ???180-350℃ | ??22.2 | ??30.4 | ??28.9 | ??29.6 | ??20.5 | ??30.1 | ??27.8 | ??19.6 | ??36.1 | ??32.0 | ??31.7 |
| ???350-500℃ | ??45.1 | ??40.8 | ??40.9 | ??39.8 | ??46.5 | ??40.0 | ??41.0 | ??45.9 | ??38.9 | ??39.4 | ??39.2 |
| ????＞500℃ | ??22.3 | ??16.1 | ??17.2 | ??15.7 | ??22.9 | ??15.6 | ??18.8 | ??24.0 | ??14.9 | ??14.5 | ??13.4 |
| Coke | ??0.8 | ??0.4 | ??0.5 | ??0.5 | ??0.9 | ??0.7 | ??0.7 | ??1.0 | ??0.4 | ??0.2 | ??0.2 |
Subtract the slag feedstock property in table 3 sand
| Project | Numerical value |
| Density (20 ℃), Kg/m 3 | ????1024.8 |
| Carbon residue, m% | ????20.73 |
| ???????C，???m％ | ????83.52 |
| ???????H，???m％ | ????10.43 |
| ???????S，???m％ | ????4.95 |
| ???????N，???m％ | ????0.35 |
| Metal content m% | |
| ???????Fe，??10 -6 | ????8.16 |
| ???????Ni，??10 -6 | ????43.4 |
| ???????V，???10 -6 | ????143.6 |
| Four proximate analysis m% | |
| Stable hydrocarbon | ????9.9 |
| Aromatic hydrocarbons | ????52.2 |
| Colloid | ????29.5 |
| Bituminous matter | ????8.4 |
Subtract slag autoclave test result in table 4 sand
| Project | ????C-2 | ????C-3 | ????C-4 | ????C-5 | ????C-10 | ????C-11 | ?????M |
| Metal content m% | ????16.2 | ????20.0 | ????13.0 | ????15.5 | ????11.7 | ????12.7 | ????9.2 |
| Temperature of reaction ℃ | ????442 | ????439 | ????435 | ????438 | ????440 | ????445 | ????438 |
| Reaction pressure Mpa | ????14 | ????10 | ????14 | ????14 | ????12 | ????14 | ????14 |
| Reaction times min | ????30 | ????30 | ????60 | ????30 | ????30 | ????60 | ????60 |
| Catalytic amount μ g/g | ????300 | ????300 | ????250 | ????250 | ????300 | ????300 | ????300 |
| Product distribution m% | |||||||
| ????＜180℃ | ????12.6 | ????11.7 | ????9.5 | ????11.6 | ????10.1 | ????12.1 | ????7.8 |
| ???180-350℃ | ????27.4 | ????28.5 | ????25.7 | ????31.3 | ????28.9 | ????29.9 | ????18.6 |
| ???350-500℃ | ????40.5 | ????39.8 | ????37.7 | ????37.8 | ????38.6 | ????37.9 | ????40.3 |
| ????＞500℃ | ????18.5 | ????19.1 | ????26.3 | ????18.5 | ????21.7 | ????19.4 | ????32.1 |
| Coke | ????1.0 | ????0.9 | ????0.8 | ????0.8 | ????0.7 | ????0.7 | ????1.2 |
The normal slag feedstock property of table 5 isolated island
| Project | The normal slag of isolated island |
| Density kg/m 3(20℃) | ????965.3 |
| Carbon residue m% | ????8.73 |
| Ultimate analysis | |
| ??????????C | ????84.78 |
| ??????????H | ????11.61 |
| ??????????S | ????1.94 |
| ??????????N | ????0.1316 |
| Metal analysis | |
| ??????????Fe | ????12.47 |
| ??????????Ni | ????24.47 |
| ??????????V | ????4.91 |
| ??????????Ca | ????14.92 |
| ??????????Cu | ????0.03 |
| ??????????Na | ????26.53 |
| Proximate analysis | |
| Saturated branch | ????31.4 |
| Fragrance divides | ????30.6 |
| Colloid | ????36.6 |
| Bituminous matter | ????1.6 |
Table 6 isolated island residual oil continuous operation result
| Project | ????C-2 | ????C-3 | ????C-4 | ????C-10 | ????C-11 |
| Metal content m% | ????16.2 | ????20.0 | ????13.0 | ????11.7 | ????12.7 |
| Temperature of reaction ℃ | ????434 | ????435 | ????437 | ????440 | ????438 |
| Reaction pressure Mpa | ????8 | ????10 | ????12 | ????10 | ????10 |
| Hydrogen-oil ratio v/v | ????1000 | ????800 | ????500 | ????1200 | ????1000 |
| Air speed h -1 | ????1.0 | ????0.8 | ????1.2 | ????0.5 | ????1.0 |
| Catalytic amount μ g/g | ????250 | ????300 | ????250 | ????300 | ????300 |
| Product distribution m% | |||||
| ?????＜180℃ | ????11.5 | ????12.8 | ????12.7 | ????13.4 | ????13.2 |
| ????180-350℃ | ????30.2 | ????29.1 | ????29.8 | ????27.8 | ????30.1 |
| ????350-500℃ | ????39.2 | ????39.9 | ????39.8 | ????41.9 | ????40.2 |
| ?????＞500℃ | ????19.1 | ????18.2 | ????17.7 | ????16.9 | ????16.5 |
Claims (10)
1, a kind of catalyzer of floating bed hydrocracking is characterized in that being one or more organic metal chelate complexs, and its metal content is 1～40 weight %.
2,, it is characterized in that described metal is selected from periodic table of elements VB, VIII, VIB or the VIIB family one or more according to the described catalyzer of claim 1.
3,, it is characterized in that described metal is one or more among Fe, Co, Ni, V, MnCr, Mo or the W according to claim 1 or 2 described catalyzer.
4,, it is characterized in that described metal content is 5～20% according to the described catalyzer of claim 1.
5,, it is characterized in that described organic sequestering agent is selected from one or more in unsaturated hydrocarbons, ketone, phenols, ethers, carboxylic acid, acyl class, oximes, amine, quinones, azo class or the sulphur hydrazone compounds according to the described catalyzer of claim 1.
6, according to the described catalyzer of claim 1, it is characterized in that described organic sequestering agent is selected from contains in hydroxyl, nitro, nitroso-group, carbonyl or the thiocarbonyl group organism one or more.
7,, it is characterized in that described organic sequestering agent is selected from methyl ethyl diketone, benzoyl acetone, dimethylglyoxime, salicylic aldehyde, 18-hat-6 ethers, dibenzo-24-hat-8-ether, diethyldithiocar bamic acid, thiooxine, disodium salt, methyl aceto acetate, N-nitroso-group β-phenylhydroxylamine amine, quadrol, protoporphyrin, dipyridyl, ferrosin, diphenyl sulfide hydrazone, citric acid, sulfosalicylic acid, eriochrome black T, chrome black A, 4-[2-pyridylazo according to the described catalyzer of claim 1]-Resorcinol and 1-[2-pyridylazo]-in the beta naphthal one or more.
8, a kind of heavy, dreg-oil suspension bed hydrogenation cracking method is reacted under weight, dreg-oil suspension bed hydrogenation cracking condition, it is characterized in that using claim 1 catalyzer, and consumption is counted 50～5000 μ g/g with metal.
9, in accordance with the method for claim 8, it is characterized in that described newborn floating bed hydrocracking condition is: 400～470 ℃ of pressure 2～20MPa, temperature, hydrogen to oil volume ratio are 200～1200, and volume space velocity is 0.2～2.0h
-1
10, in accordance with the method for claim 8, it is characterized in that described catalyzer add-on is 200～400 μ g/g.
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| CN110237850A (en) * | 2018-03-07 | 2019-09-17 | 中国石油天然气股份有限公司 | Preparation method of hydrocracking catalyst |
| CN110237851A (en) * | 2018-03-07 | 2019-09-17 | 中国石油天然气股份有限公司 | Oil-soluble catalyst and preparation method and application thereof |
| CN110237862A (en) * | 2018-03-07 | 2019-09-17 | 中国石油天然气股份有限公司 | Method for preparing hydrocracking catalyst |
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| CN110237866A (en) * | 2018-03-07 | 2019-09-17 | 中国石油天然气股份有限公司 | Preparation method of oil-soluble catalyst |
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-
2001
- 2001-01-05 CN CN 01106048 patent/CN1132910C/en not_active Expired - Lifetime
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| CN102250045A (en) * | 2010-05-21 | 2011-11-23 | 复旦大学附属华山医院 | Mycobacterium tuberculosis resisting compounds, and applications thereof |
| CN102909080A (en) * | 2011-08-03 | 2013-02-06 | 中国石油大学(华东) | Oil-soluble binary compound catalyst for hydrocracking high-sulfur low-quality heavy-oil slurry bed |
| CN107057756A (en) * | 2017-06-23 | 2017-08-18 | 北京中科诚毅科技发展有限公司 | A kind of all-round bed hydroprocessing technique |
| CN110240930A (en) * | 2018-03-07 | 2019-09-17 | 中国石油天然气股份有限公司 | Preparation method of oil-soluble catalyst |
| CN110237850A (en) * | 2018-03-07 | 2019-09-17 | 中国石油天然气股份有限公司 | Preparation method of hydrocracking catalyst |
| CN110237851A (en) * | 2018-03-07 | 2019-09-17 | 中国石油天然气股份有限公司 | Oil-soluble catalyst and preparation method and application thereof |
| CN110237862A (en) * | 2018-03-07 | 2019-09-17 | 中国石油天然气股份有限公司 | Method for preparing hydrocracking catalyst |
| CN110237861A (en) * | 2018-03-07 | 2019-09-17 | 中国石油天然气股份有限公司 | Preparation method of hydrocracking catalyst and inferior heavy oil/residual oil slurry bed hydrogenation reaction method |
| CN110237866A (en) * | 2018-03-07 | 2019-09-17 | 中国石油天然气股份有限公司 | Preparation method of oil-soluble catalyst |
| CN108772101A (en) * | 2018-08-16 | 2018-11-09 | 南京工业大学 | High-efficiency metal complex molecular catalyst and preparation and application thereof |
| WO2023071930A1 (en) * | 2021-10-25 | 2023-05-04 | 中国石油化工股份有限公司 | Non-supported hydrogenation catalyst, and preparation method therefor and use thereof |
| WO2023071936A1 (en) * | 2021-10-25 | 2023-05-04 | 中国石油化工股份有限公司 | Non-supported bimetallic hydrogenation catalyst, and preparation method therefor and application thereof |
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