CN1445339A - High decentralization type catalyzer utilized in suspension bed isocracking process - Google Patents
High decentralization type catalyzer utilized in suspension bed isocracking process Download PDFInfo
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Abstract
A high-dispersed catalyst for hydrocracking of suspension bed is prepared through dissolving or dispersing one or more of Cr, Ag, Au, Zn, Cd and Hg in alcohol, water, or aqueous solution of alcohol.
Description
Technical field:
The invention belongs to a kind of catalyzer of the hydrocracking process of suspended bed in the petroleum refining process, also can be used for the hybrid process process of gelatin liquefaction process and coal and oil.
Background technology:
Floating bed hydrocracking is meant that catalyzer is evenly dispersed in the raw material, is in the hydrocracking process of suspended state in reactor.Catalyzer commonly used has inorganic salt, organic salt or the heteropolyacid salt of transition element such as Co, Mo, Ni, Fe, W, Mn, and the aqueous solution of these materials or organic compound are dispersed in the raw material, have just formed the catalytic active substance of hydrocracking process of suspended bed.
Chinese patent application 95118354.0,96102879.3 is used the solution compositing catalyst that contains molybdenum, nickel, phosphorus; Chinese patent 96102880.7 uses the solution compositing catalyst that contains molybdenum, nickel, cobalt, phosphorus; Chinese patent 97121791.2 uses the mixed aqueous solution of nickelous nitrate, manganous nitrate, iron nitrate, Xiao Suangu as catalyzer; Chinese patent application 97121844.7 uses molybdenum, nickel, cobalt, the tungsten aqueous solution as catalyzer; Chinese patent 97121845.5 uses molybdenum, nickel, the cobalt aqueous solution as catalyzer; Chinese patent application 99113301.3 uses the aqueous solution of two or more metallic compounds in periodic table of elements VIB, VIIB and the group VIII as catalyzer, comprising the aqueous solution of molybdenum, nickel, cobalt, tungsten, chromium, iron; Suspension bed residual oil hydrogenation catalyzer in the Chinese patent application 00110715.1 uses the aqueous solution of molybdenum, nickel, phosphorus as catalyzer; Weight among the Chinese patent application 00110716.X, dreg-oil suspension bed catalyzer use the aqueous solution of molybdenum, nickel, phosphorus as catalyzer; The aqueous solution that adopts molybdenum, nickel, tungsten, cobalt in the Chinese patent application 00123153.7 is catalyzer; Chinese patent application 01109276.9 adopts the solution compositing catalyst of iron, nickel, cobalt, molybdenum.The common issue with that the catalyzer that relates in the above-mentioned patent application exists is: 1. catalyzer is the aqueous solution that contains metal, and raw material is a heavy raw oil, and the two is immiscible.Metallic catalyst constituents is difficult in the effect that reaches high dispersive in the heavy raw oil, and the utilization ratio of metallic catalyst constituents is low.2. aqueous catalyzer also must remove water by brute force stirring, shear agitation or after being distributed in the mink cell focus under the effect of tensio-active agent, with hydrogen partial pressure that improves reactive system or the Hydrobon catalyst of protecting post-processing unit.3. the disposable often use of the catalyzer of floating bed hydrocracking, the aqueous solution that uses molybdenum, nickel, cobalt, tungsten etc. is as catalyzer, and cost is too high, is restricted in industrial application.
Chinese patent application 00110711.9 is used one or more metals in periodic table of elements VIB, VIIB and the group VIII and is contained the formed complex compound of heteroatomic heterocycle sulfo group compound, and metallic element wherein includes iron, cobalt, nickel, chromium, molybdenum, tungsten; Chinese patent application 00123148.0 is used the promotor of one or more compounds of metal in the periodic table of elements group VIII as catalyzer in the floating bed hydrogenation process, wherein includes muriate, nitrate, prussiate, oxide compound, halohydrocarbon, ethers, amine, quinones, the azo class of Ru, Rh, Pd, Os, Ir, Pt and contains the organism of carbonyl, thiocarbonyl group.Chinese patent application 01106013.1 is about a kind of hydrocracking catalyst for oil-soluble suspension bed, two or more metals in use periodic table of elements VIB, VIIB and the group VIII and the compound of phenylhydroxylamine and derivatives reaction gained thereof, wherein metallic element includes molybdenum and tungsten.With the metallic compound that contains organic group as disperse type catalyzer, the dispersion effect in mink cell focus be improved significantly because it is a kind of oil-soluble material, can dissolve each other with stock oil.Directly as product, do not need to separate after the organic group reaction.But the problem that it exists is: relative and atoms metal, the molecular weight of organic group is very big, adds the very metal of small concentration, needs to add relatively large organometallic compound.After organometallic compound enters into reactive system, just be decomposed, the main effect of organic group is the dispersed metal ion.Use the effect of oil-soluble catalyst better, but the cost of catalyzer also is higher than water-soluble catalyst far away than water-soluble catalyst.
In the high dispersive type catalyzer involved in the present invention, contain alcohols, water or alcohols and the aqueous solution, contain one or more of material of copper, silver, gold, zinc, cadmium, mercury element simultaneously.High dispersive type catalyzer also makes the alkene of generation and the alcohols in the catalyzer react when promoting that raw material generation cracking generates alkene, generates high-octane oxygenatedchemicals, has both reduced the olefin(e) centent of gasoline, has improved the octane value of gasoline again.Because high dispersive type catalyzer can dissolve each other with raw material, the dispersity in raw material is very high, and catalytic activity height, conversion of raw material and liquid yield are also just very high.The alcohols that contains in the high dispersive type catalyzer involved in the present invention be transformed into higher gasoline of value and diesel oil in reaction process, so the cost of this catalyzer is very low.
Summary of the invention:
The invention discloses a kind of high dispersive type catalyzer that is used for hydrocracking process of suspended bed, it is characterised in that this catalyzer contains following two kinds of components at least simultaneously: (a) solution of alcohols or water or alcohols and water; (b) contain one or more of material of copper, silver, gold, zinc, cadmium, mercury element.This high dispersive type catalyzer has overcome the shortcoming that existing water-soluble catalyst and raw material can not dissolve each other, and is expensive unlike oil-soluble catalyst again, is a kind of high dispersive type catalyzer that is suitable for industrial application.
After raw material and the high dispersive type catalyst mix, high dispersive type catalyzer high dispersing is in suspended state in raw material.Under the floating bed hydrocracking reaction conditions, high dispersive type catalyzer is promoting the raw material cracked simultaneously, and the alkene that also promotes alcohols and raw material cracking to generate reacts, and generates octane value RON at 110 left and right sides oxygenatedchemicalss.So both reduce the content of alkene, improved the octane value and the stability of gasoline again.
Embodiment:
Floating bed hydrocracking technology usually is used for the processing of inferior raw material, catalyzer is used the aqueous solution, organic compound, inorganic or organic complex compound, the heteropolyacid salt of transition element such as Co, Mo, Ni, Fe, W, Mn always, natural ore powder art, coal dust, special earth powder and the spent catalyst powder of other technological process.These said catalyzer are dispersed in the raw material, and major part is in suspended state.
Catalyzer mainly plays two effects in hydrocracking process of suspended bed: 1. promote hydrogen transference, produce the condensation that hydroperoxyl radical suppresses the condensed ring free radical of cracking reaction generation, just suppress the generation of coke; 2. as the medium that carries coke.Certainly lead to coke in the reaction process, if do not carry its place, they will flock together and form bulk, finally stop up reactor.Catalyzer adds reactor and the subsequent disposal system equally also can stopped up too much.
Think that usually radical reaction mechanism is deferred in the floating bed hydrocracking reaction, reaction process is a kind of based on heat cracking reaction, and hydrogenation reaction and isomerization reaction are the process of assisting.In hydrocracking process of suspended bed, the isomerisation degree of product is very low, because used catalyzer usually is no acidic, even acidity is arranged, the ratio of catalyzer and stock oil is too little, and the ratio of isomerization reaction is also well below the ratio of heat cracking reaction.Therefore, contain a large amount of alkene in the gasoline fraction.
When high dispersive type catalyzer provided by the present invention mixed with raw material, because this catalyzer can dissolve each other with raw material, it can be dispersed in the raw material with high dispersity.High dispersive type catalyzer is in the fcc raw material cracked while, and also the alkene of catalyzing alcohols and raw material cracking generation reacts, and generates oxygenatedchemicals.The octane value RON of these oxygenatedchemicalss is generally about 110.Therefore high dispersive type catalyzer provided by the present invention, catalytic activity height not only, and can improve the octane value of product gasoline.
The alcohols that contains in the high dispersive type catalyzer provided by the present invention is one or more a mixture of the alcohols of no more than 10 carbon atoms in the molecule, and preferred alcohols is methyl alcohol and ethanol.
The water that contains in the high dispersive type catalyzer provided by the present invention is that molecular formula is H
2The water that contains two hydrogen atoms and a Sauerstoffatom in O, each water molecules, i.e. Chang Gui process water.
The material that contains copper, silver, gold, zinc, cadmium, mercury element in the high dispersive type catalyzer provided by the present invention is meant and contains copper, silver, gold, zinc, cadmium, mercury element, and can form inorganic salt, organic salt, complex compound or the inner complex of true solution, milk sap or suspension liquid with the solution of ionic condition, molecularity, hydration status, complex status, polymolecular polymerization state and above-mentioned alcohols or water or alcohols and water.The material that preferably contains copper and zinc element.The material that most preferably contains cupric nitrate.
High dispersive type catalyzer provided by the present invention is with the difference of traditional floating bed hydrocracking high dispersive type catalyzer:
(a) high dispersive type catalyzer involved in the present invention contains following two kinds of components: the 1. solution of alcohols or water or alcohols and water at least simultaneously; 2. one or more of material that contain copper, silver, gold, zinc, cadmium, mercury element.Existing floating bed hydrocracking high dispersive type catalyzer mainly contains two kinds: the inorganics or the organism that contain metallic element are dissolved in the water-soluble catalyst that forms in the water; The larger molecular organics that contains metallic element, promptly so-called oil-soluble catalyst.Catalyzer provided by the present invention is that the inorganics or the organism that contain metallic element are dissolved in the solution of alcohols or water or alcohols and water, both can the dissolving each other with water of formation, the high dispersive type catalyzer that can dissolve each other with oil again.
(b) catalyst action mechanism difference.High dispersive type catalyzer involved in the present invention is promoting the raw material cracked simultaneously, also promotes the alkene of generation and the alcohols in the catalyzer to react, generate high-octane oxygenatedchemicals, reach reduction alkene, the purpose of boosting of octane rating, the octane value RON of gasoline reaches more than 85.And use existing high dispersive type catalyzer, and the octane value of product gasoline is low, and about 70～75;
The present invention further describes with reference to the following example, but these embodiment should not be considered to limit use range of the present invention.
Raw material adopts boiling point at 360 ℃～520 ℃ vacuum gas oil, and its character sees Table 1.
Table 1 Application Example feedstock property
| Boiling range scope/℃ density (20 ℃)/gcm -3Viscosity (100 ℃)/mm 2·s -1Condensation point/℃ carbon residue/m% basic nitrogen/μ gg -1 | ????360～520 ????0.9182 ????7.1 ????10 ????0.10 ????1370 |
| H/C atomic ratio S/m% N/m% | ????1.73 ????0.079 ????0.46 |
| Saturated part/m% fragrance part/m% colloid/m% | ????75.8 ????17.1 ????7.1 |
Testing apparatus is the medium-sized long run test device of 3 liters loop reactor for using volume; The temperature of floating bed hydrocracking reactor is 430 ℃～450 ℃, liquid-volume hourly space velocity (LHSV) 0.6～1.0h
-1The hydrogen dividing potential drop is 10MPa～11MPa; Alcohols in the high dispersive type catalyzer adopts methyl alcohol; The material that contains copper, silver, gold, zinc, cadmium, mercury element adopts the cupric nitrate crystal; Also add vulcanizing agent dithiocarbonic anhydride in addition.Conversion of raw material is higher than 95%, and liquid yield is 90%.Now illustrate as follows:
(1) high dispersive type catalyzer is formed
With cupric nitrate crystal [Cu (NO
3)
22H
2O] join in the methanol aqueous solution, in the methanol aqueous solution of this cupric nitrate, add dithiocarbonic anhydride then.The blue clear solution that forms is exactly a high dispersive type catalyzer used in the application example.In this high dispersive type catalyzer, copper accounts for 3m%～4m%, and water accounts for 10m%, and dithiocarbonic anhydride is 2: 1 with cupric nitrate crystalline molecule number ratio.
(2) process feeds composition, flow process and products distribution
Test with 97.42% is with the above-mentioned high dispersive type catalyzer of vacuum gas oil and 2.58%, by entering process furnace after the fresh feed pump mixing.Need to inject hydrogen partial before the process furnace, to improve the flow velocity of raw material in boiler tube.Vacuum gas oil after the heating and high dispersive type catalyzer enter full backmixed reactor and react.After some hydrogen heats separately in addition, enter reactor.Reacted product is discharged from reactor, and through obtaining the gasoline that boiling point is lower than 180 ℃ after the fractionation, 180～350 ℃ of diesel oil and boiling point are higher than 350 ℃ residue tail oil.
The medial temperature of reactor is respectively 430 ℃, 440 ℃ and 450 ℃.When temperature of reaction is 450 ℃, the amount of methyl alcohol in the deduction high dispersive type catalyzer, the transformation efficiency of vacuum gas oil is 95.66%, the yield of gasoline and diesel oil is 90.30%, the weight ratio of diesel oil and gasoline (diesel and gasoline ratio) is 1.85, boiling point is higher than sulphur that contains in 350 ℃ the tail oil and the sulphur that is removed, and accounts for 82.27% of total sulfur content in the charging.See Table 2 and table 3.
Table 2 feed composition and products distribution
| Feed composition | The product that temperature of reaction is 430 ℃ is formed | The product that temperature of reaction is 440 ℃ is formed | The product that temperature of reaction is 450 ℃ is formed | |
| High dispersive type catalyzer/m% | ??2.58 | ?????- | ?????- | ??????- |
| ??C 1～C 4Gas/m% | ????- | ????5.63 | ????5.90 | ?????5.95 |
| ??C 5～180 ℃ of gasoline/m% | ????- | ????20.45 | ????27.31 | ?????31.73 |
| 180～350 ℃ of diesel oil/m% | ????- | ????46.46 | ????53.11 | ?????58.57 |
| ＞350 ℃ of decompressed wax oil/m% | ??97.42 | ????27.91 | ????14.14 | ?????4.23 |
| Wax oil transformation efficiency/m% | ????- | ????71.35 | ????85.49 | ?????95.66 |
The sulphur content of table 3 charging and product (450 ℃ of temperature of reaction)
| The charging wax oil | ????C 5～180 ℃ of product gasoline | 180～350 ℃ of product diesel oil | |
| Weight of material percentage ratio/m% | ????97.42 | ?????31.73 | ?????58.57 |
| Sulphur content/m% | ????0.079 | ?????0.0181 | ?????0.0135 |
| Account for charging total sulfur percentage ratio/m% | ????100 | ?????7.46 | ?????10.27 |
(3) character of gasoline, diesel oil
When table 4, table 5 are 450 ℃ for temperature of reaction, the gasoline of generation and the character of diesel oil.The aromaticity content of gasoline, olefin(e) centent, sulphur content can both reach the new gasoline standard of country, and octane value RON is 89.The sulphur content of diesel oil is also very low, and cetane value reaches country and is not less than 40 standard, can further improve cetane value by hydrofining.
The character of table 4 product gasoline
| Aromaticity content/m% | ????17.6 |
| Normal paraffin content/m% | ????15.4 |
| Isoparaffin/m% | ????19.5 |
| Naphthenic hydrocarbon/m% | ????11.8 |
| Alkene/m% | ????14.3 |
| Methyl alcohol/m% | ????0.024 |
| Oxygenatedchemicals/m% | ????10.0 |
| Octane value RON | ????89 |
| Sulphur content/m% | ????0.0181 |
The character of table 5 product diesel oil
| Density (20 ℃)/gcm -3 | ????0.8824 |
| Aniline point/℃ | ????55 |
| Sulphur content/m% | ????0.0135 |
| Cetane index | ????41 |
| Condensation point/℃ | ????-38 |
(4) distribution situation of catalyzer in the floating bed hydrocracking reactor
With reaction product, the high dispersive type catalyzer of the reaction of discharging from the floating bed hydrocracking reactor still has high dispersity, and diameter surpasses 80% less than the granule number of the catalyzer of 1 μ m.Table 6 is with the granules of catalyst in the product liquid after the laser particle analyzer analytical reaction, the particle size distribution data that obtains.Granules of catalyst is little, be evenly distributed one of reason that this also is the catalyst activity height, feed stock conversion is high.
The grain of catalyzer is released and is distributed and the granule number distribution in table 6 reaction product
| Particle size distribution range/μ m | Relative granule number/% | Particle size distribution range/μ m | Relative granule number/% |
| ????＜0.375 | ?????5.12 | ?????1.520～1.668 | ????1.44 |
| ????0.375～0.412 | ?????6.81 | ?????1.668～1.832 | ????1.08 |
| ????0.412～0.452 | ?????7.73 | ?????1.832～2.011 | ????0.79 |
| ????0.452～0.496 | ?????8.71 | ?????2.011～2.207 | ????0.57 |
| ????0.496～0.545 | ?????8.92 | ?????2.207～2.423 | ????0.41 |
| ????0.545～0.598 | ?????8.61 | ?????2.423～2.660 | ????0.28 |
| ????0.598～0.656 | ?????8.10 | ?????2.660～2.920 | ????0.20 |
| ????0.656～0.721 | ?????7.45 | ?????2.920～3.205 | ????0.14 |
| ????0.721～0.791 | ?????6.73 | ?????3.205～3.519 | ????0.09 |
| ????0.791～0.868 | ?????5.97 | ?????3.519～3.863 | ????0.07 |
| ????0.868～0.953 | ?????5.19 | ?????3.863～4.240 | ????0.05 |
| ????0.953～1.047 | ?????4.41 | ?????4.240～4.655 | ????0.03 |
| ????1.047～1.149 | ?????3.68 | ?????4.655～5.110 | ????0.03 |
| ????1.149～1.261 | ?????3.01 | ?????5.110～5.610 | ????0.02 |
| ????1.261～1.384 | ?????2.41 | ?????5.610～6.158 | ????0.01 |
| ????1.384～1.520 | ?????1.88 | ?????＞6.158 | ????0.06 |
(5) cost of catalyzer
Should be lower than the price that methyl alcohol participates in the gasoline of reaction back generation with the price of the methyl alcohol in the example.Therefore, the cost of high dispersive type catalyzer is very low, even can accomplish zero cost.In certain scope, the high dispersive type catalytic amount of adding is big more, and the cost of catalyzer is just more little, and the octane value of gasoline is also high more.This has fundamentally solved the cost problem of the catalyzer of restriction floating bed hydrocracking technology.
Claims (10)
1. high dispersive type catalyzer that is used for hydrocracking process of suspended bed, it is characterised in that contains following two kinds of components at least simultaneously in this catalyzer: (a) solution of alcohols or water or alcohols and water; (b) contain one or more of material of copper, silver, gold, zinc, cadmium, mercury element.
2. catalyzer according to claim 1 is characterized in that said alcohols is one or more the mixture that contains the alcohol of 1 to 10 carbon atom in the molecule.
3. catalyzer according to claim 1 and 2, it is characterised in that said alcohols is one or more the mixture in methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, isomery butanols, isomery amylalcohol, the isomery hexanol.
4. catalyzer according to claim 1 and 2, it is characterised in that said alcohols is one or both the mixture in methyl alcohol and the ethanol.
5. catalyzer according to claim 1, the molecular formula that it is characterized in that said water is H
2O contains two hydrogen atoms and a Sauerstoffatom in each water molecules.
6. catalyzer according to claim 1, the solution that it is characterized in that said alcohols and water are one or more of claim 1,2,3,4 described alcohols, with the solution of claim 1 or 5 described water formation.
7. catalyzer according to claim 1, it is characterized in that the said material that contains copper, silver, gold, zinc, cadmium, mercury element is meant contains copper, silver, gold, zinc, cadmium, mercury element, and can form inorganic salt, organic salt, complex compound or the inner complex of true solution, milk sap or suspension liquid with the solution of ionic condition, molecularity, hydration status, complex status, polymolecular polymerization state and claim 1,2,3,4,5 or 6 said alcohols or water or alcohols and water.
8. according to claim 1 or 7 described catalyzer, it is characterized in that in the said material that contains copper, silver, gold, zinc, cadmium, mercury element, wherein a kind of copper bearing material is cupric nitrate or cupric nitrate crystal, wherein a kind of argentiferous material is a Silver Nitrate, and wherein a kind of zinciferous material is a zinc nitrate.
9. catalyzer according to claim 1, it is characterized in that two kinds of components that contain at least simultaneously in the described catalyzer are like this preparations:, be dissolved in or be dispersed in the solution of claim 1,2,3,4,5 or 6 described alcohols or water or alcohols and water with claim 1, the 7 or 8 described materials that contain copper, silver, gold, zinc, cadmium, mercury element one or more.
10. catalyzer according to claim 1, the characteristics that it is characterized in that the hydrocracking process of suspended bed that this catalyzer can be applied to are: in the raw material gaseous product that cracking generates in described hydrocracking process of suspended bed, the cumulative volume of methane, ethane and three kinds of gases of ethene is greater than the cumulative volume of propane, propylene, butane and the butylene gas of positive structure and various isomer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210195B (en) * | 2006-12-27 | 2012-05-30 | 中国石油化工股份有限公司 | Hydrocracking method for more producing chemical industry light oil from poor heavy raw material |
| CN103285928A (en) * | 2012-02-22 | 2013-09-11 | 中国石油化工股份有限公司 | Iron-oxide-ore-containing heavy oil hydrogenation catalyst, and preparation and application thereof |
| CN103285929A (en) * | 2012-02-22 | 2013-09-11 | 中国石油化工股份有限公司 | Bauxite-containing heavy oil hydrogenation catalyst, and preparation and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2113047T3 (en) * | 1993-12-28 | 1998-04-16 | Ube Industries | PROCESS TO PRODUCE DIOLIC COMPOUNDS. |
| US5741415A (en) * | 1994-09-27 | 1998-04-21 | Chevron U.S.A. Inc. | Method for the demercaptanization of petroleum distillates |
| CN1053460C (en) * | 1996-04-16 | 2000-06-14 | 中国石油化工集团公司 | Dispersive catalyst for hydrogenation of heavy and residual oil |
| CN1151239C (en) * | 2001-07-02 | 2004-05-26 | 中国石油化工股份有限公司 | Process for lightening heavy oil or residual oil |
-
2003
- 2003-04-07 CN CNB031121004A patent/CN100351347C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210195B (en) * | 2006-12-27 | 2012-05-30 | 中国石油化工股份有限公司 | Hydrocracking method for more producing chemical industry light oil from poor heavy raw material |
| CN103285928A (en) * | 2012-02-22 | 2013-09-11 | 中国石油化工股份有限公司 | Iron-oxide-ore-containing heavy oil hydrogenation catalyst, and preparation and application thereof |
| CN103285929A (en) * | 2012-02-22 | 2013-09-11 | 中国石油化工股份有限公司 | Bauxite-containing heavy oil hydrogenation catalyst, and preparation and application thereof |
| CN103285928B (en) * | 2012-02-22 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation catalyst containing ferric oxide ore and Synthesis and applications thereof |
| CN103285929B (en) * | 2012-02-22 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation catalyst of aluminiferous ore and Synthesis and applications thereof |
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