CN101108363A - Manufacturing method of catalyzer used for low quality light oil catalytic reforming and application thereof - Google Patents
Manufacturing method of catalyzer used for low quality light oil catalytic reforming and application thereof Download PDFInfo
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- CN101108363A CN101108363A CNA2007100116898A CN200710011689A CN101108363A CN 101108363 A CN101108363 A CN 101108363A CN A2007100116898 A CNA2007100116898 A CN A2007100116898A CN 200710011689 A CN200710011689 A CN 200710011689A CN 101108363 A CN101108363 A CN 101108363A
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Abstract
The invention provides a preparation method and the application of a low quality light oil catalyzing modifying catalyst. The catalyst is prepared by taking a nanometer ZSM-5 molecular sieve as a generatrix, aluminium oxide as a carrier to load such active components as the oxides of La, Ni, Co, Mu and Tu, etc., using citric acid to soak and modify, and then drying and calcining. For modifying catalytically cracked gasoline (catalytically cracked gasoline, coke gasoline and straight-run gasoline), the catalyst can substantially reduce the content of olefin and sulfur in gasoline with low loss in octane value; for modifying catalytically cracked gasoline and straight-run gasoline, the catalyst can greatly improve the octane value of petroleum while reducing the content of sulfur.
Description
Technical field
The present invention relates to a kind of preparation method and application that is used for low quality light oil (catalytically cracked gasoline, coker gasoline and direct steaming gasoline) catalyst for performing catalytic reforming, belong to the concise technical field of petroleum chemical industry oil product.
Background technology
Catalytically cracked gasoline, coker gasoline and direct steaming gasoline all are the light-end products that produce in the petroleum refining process.Olefin(e) centent height in the catalytically cracked gasoline (40～55vol%), sulfur content height (200～1500 μ g/g), the octane number of coker gasoline and direct steaming gasoline is low, research octane number (RON) is generally 50～60, along with the raising day by day of clean gasoline standard, above-mentioned oil product could be as the blend component of merchantable gasoline after must passing through catalytic reforming.
US 5,865, and 988 have introduced a kind of low-quality gasoline upgrading technology of Mobil company exploitation.This process using two-step method is carried out upgrading to gasoline, at first with raw gasoline by containing Co-Mo/Al
2O
3The bed of catalyst, hydrogenation and removing sulfide makes part alkene saturated simultaneously; Then with the product that generates previously by containing the bed of ZSM-5 catalyst, to recover the saturated and loss of octane number that causes of in hydrogenation process alkene.US 5,362,376 technologies of having introduced a kind of catalyzed gasoline hydrogenation desulfurization and having selected shape hydrocracking two-stage catalytic agent combination.The catalytically cracked gasoline heavy distillat that is characterized in prefractionation is after hydrodesulfurization, pass through the NiO/HZSM-5 molecular sieve catalyst shape slective cracking of mesopore, acidity again, thereby recover because of the saturated loss of octane number that causes of hydrogenation of olefins in the hydrodesulfurization, and then be in harmonious proportion with light fraction.Above-mentioned hydrodesulfurization is developed at the characteristics of its olefin(e) centent lower (about 20vol%), aromatic hydrocarbons higher (about 40vol%).
CN 1,690, and 171 disclose a kind of loaded catalyst and preparation and the application in desulfurizing and reducing olefine for gasoline.This catalyst will from liquid load on the appropriate carriers, can make the sulfide that contains alkene gasoline, especially thiophenes and alkene carry out the higher alkylthrophene compounds of alkylated reaction generation boiling point, thereby can the higher boiling sulfur compound effectively be separated with gasoline fraction by distillation, the gasoline fraction olefin(e) centent of distillation back gained descends 5%～10%, desulfurization degree reaches 90%, 1～2 unit of research octane number (RON) decline.
CN 1,600, and 836 have introduced the method that the direct steaming gasoline upgrading prepares gasoline with low olefine content, direct steaming gasoline and C 4 olefin cut mixed the back contact with the HZSM-5 catalyst, can produce the low gasoline component of high-octane rating and olefin(e) centent.
The patent CN of Dalian University of Technology 1,350,051 have introduced a kind of method of modifying inferior gasoline to prepare clean gasoline, and it is catalyst that this method adopts nanocrystal ZSM-5 modified molecular screen, can significantly reduce olefin content in gasoline and sulfur content, and octane number does not reduce substantially.
Summary of the invention
The objective of the invention is at CN 1,350, on the 051 patent basis, propose to be used for low quality light oil catalytic reforming Preparation of catalysts methods and applications.
Technical scheme of the present invention is that catalyst is the nano-ZSM-5 molecular sieve of 60%-80%, the carrier A l of weight percentage 10%-30% by weight percentage
2O
3, the lanthanide rare metal oxide of weight percentage 1%-20% and transition metal oxide form, and floods modification in molar concentration is the organic acid of 0.1-2.0mol/L, drying, roasting are made.
In the catalyst of the present invention, the grain size of nano-ZSM-5 molecular sieve is 20-100nm.The lanthanide rare metal oxide is selected from La
2O
3, transition metal oxide is selected from NiO, CoO, WO
3And MoO
3In one or more.Organic acid is a citric acid.
Preparation process of the present invention is: at first press CN 1,240,193 described method synthesis of nano ZSM-5 molecular sieves, be raw material promptly with waterglass, Ludox, aluminum sulfate, in the presence of organic amine, quaternary ammonium salt or template agent, add alkali, salt, water and crystal seed, by the certain molar ratio batching, through variable temperature crystallization, separation, washing, drying, make the nanocrystal molecular sieve.
With weight percentage is the carrier A l of 60%-80% nano-ZSM-5 molecular sieve and weight percentage 10%-30%
2O
3Mix, adding weight percentage is the binding agent sesbania powder of 1.0%-5.0%, adds volume ratio 1%-10%HNO again
3Aqueous solution is even, extruded moulding, temperature programming to 540 ℃ roasting 3-10 hour; Putting into molar concentration after the cooling again is the 0.1-1.0mol/L aqueous ammonium nitrate solution, presses solid-to-liquid ratio (g/ml) 1-3: 10 normal temperature dippings 2 times, and each 4-8 hour, spend deionised water, nanometer HZSM-5 catalyst is made in filtration, dry, roasting.The HZSM-5 catalyst is carried out hydrothermal treatment consists modification, metal oxide-loaded modification and the modification of citric acid dipping successively, makes composite modified catalyst:
Nanometer HZSM 5 catalyst are put into the hydrothermal treatment consists stove, at 400-700 ℃, with air speed 0.1-1h
-1Fed steam treatment 2-10 hour; Again it is put into lanthanum nitrate aqueous solution, normal temperature dipping 4-10 hour, 90-120 ℃ of oven dry, 540 ℃ roasting 3-10 hour, put into the nitrate or the sulfate solution of nickel or cobalt metal after the cooling, normal temperature dipping 4-10 hour, 90-120 ℃ of oven dry, 540 ℃ roasting 3-10 hour, put into ammonium heptamolybdate or ammonium metatungstate aqueous solution after the cooling again, normal temperature dipping 4-10 hour, 90-120 ℃ of oven dry, 540 ℃ roasting 3-10 hour; Putting into concentration after the cooling again is the 0.1-2.0mol/L aqueous citric acid solution, normal temperature dipping 4-10 hour, and 90-120 ℃ of oven dry, temperature programming to 540 ℃ roasting 3-10 hour.The composite modified catalyst of the present invention's preparation is applied to the catalytic reforming of catalytically cracked gasoline, coker gasoline and direct steaming gasoline.
The invention has the beneficial effects as follows, the catalyst that is used for the low quality light oil upgrading of the present invention's preparation, have the aromatisation of good isomerization, appropriateness and the function that removes olefin(e) centent and sulfur content in the oil product, the upgrading that is used for catalytically cracked gasoline, alkene in the gasoline can be converted into high-octane isoparaffin and aromatic hydrocarbons, with the saturated loss that cause octane number of compensation owing to olefin(e) centent.The upgrading that is used for coker gasoline and direct steaming gasoline when reducing sulfur in gasoline content, can be converted into high-octane isoparaffin and aromatic hydrocarbons with low-octane n-alkane, has therefore increased substantially the octane number of oil product.
The specific embodiment
Embodiment 1
Take by weighing 400g by the synthetic nano-ZSM-5 (SiO of patent CN 1,240,193 described methods
2/ Al
2O
3Mol ratio is 25.5), 100g Al
2O
3With 1.2g binding agent sesbania powder, and their ground and mixed is even, adding concentration is the dilute nitric acid solution of 9.8g/100ml, grind evenly the back is extruded into the bar that diameter is 1.5mm on banded extruder.After room temperature is dried, 120 ℃ of dryings 6 hours, temperature programming to 540 ℃ roasting 3 hours.After the cooling, putting into molar concentration is the 0.4mol/L ammonium nitrate solution, by 1: 10 normal temperature dipping of solid-to-liquid ratio (g/ml) 2 times, each 6 hours, spend deionised water to neutral, filter, after room temperature dries, 120 ℃ of dryings 6 hours, nanometer HZSM-5 catalyst is made in temperature programming to 540 ℃ roasting 3 hours.
Embodiment 2
Take by weighing the nanometer HZSM-5 catalyst 100g that makes by embodiment 1, put into the constant temperature zone of hydrothermal treatment consists stove, at 500 ℃, with air speed 0.2h
-1Fed steam treatment 3 hours.Above-mentioned catalyst is taken out in control cooling back, temperature programming to 540 ℃, roasting 3 hours.
Embodiment 3
Take by weighing the HZSM-5 catalyst 10g of the hydrothermal treatment consists modification that makes by embodiment 2, put into 18ml and contain 0.30g La
2O
3Lanthanum nitrate aqueous solution in, room temperature dipping 5 hours, 120 ℃ of dryings 6 hours, temperature programming to 540 ℃ roasting 6 hours; Put into the nickel nitrate aqueous solution that 18ml contains 0.20g NiO after the cooling, room temperature dipping 5 hours, 120 ℃ of dryings 6 hours, temperature programming to 540 ℃ roasting 6 hours; Put into 18ml after the cooling and contain 0.80g MoO
3The ammonium heptamolybdate aqueous solution in, room temperature dipping 4 hours, 120 ℃ of dryings 6 hours, temperature programming to 540 ℃ roasting 4 hours; Put into the aqueous citric acid solution that the 18ml molar concentration is 0.5mol/L after the cooling, room temperature dipping 4 hours, 120 ℃ of dryings 6 hours, temperature programming to 540 ℃ roasting 4 hours made 3.0wt%La
2O
3-2.0wt%NiO-8.0wt%MoO
3/ HZSM-5 composite modified catalyst.
Embodiment 4
Take by weighing the HZSM-5 catalyst 25g of the hydrothermal treatment consists modification that makes by embodiment 2, put into 45ml and contain 0.50g La
2O
3Lanthanum nitrate aqueous solution in, room temperature dipping 5 hours, 120 ℃ of dryings 6 hours, temperature programming to 540 ℃ roasting 6 hours; Put into the cobalt nitrate aqueous solution that 45ml contains 0.50g CoO after the cooling, room temperature dipping 5 hours, 120 ℃ of dryings 6 hours, temperature programming to 540 ℃ roasting 6 hours; Put into the aqueous citric acid solution that the 45ml molar concentration is 0.25mol/L after the cooling, room temperature dipping 4 hours, 120 ℃ of dryings 6 hours, temperature programming to 540 ℃ roasting 4 hours; Put into 45ml after the cooling and contain 2.50g MoO
3The ammonium heptamolybdate aqueous solution in, room temperature dipping 4 hours, 120 ℃ of dryings 6 hours, temperature programming to 540 ℃ roasting 4 hours, 2.0wt%La
2O
3-2.0wt%CoO-10wt%MoO
3/ HZSM-5 composite modified catalyst.
Embodiment 5
Take by weighing the HZSM-5 catalyst 50g of the hydrothermal treatment consists modification that makes by embodiment 2, put into 90ml and contain 0.50g La
2O
3Lanthanum nitrate aqueous solution in, room temperature dipping 5 hours, 120 ℃ of dryings 6 hours, temperature programming to 540 ℃ roasting 6 hours; Put into the aqueous citric acid solution that the 90ml molar concentration is 0.4mol/L after the cooling, room temperature dipping 4 hours, 120 ℃ of dryings 6 hours, temperature programming to 540 ℃ roasting 4 hours; Put into the nickel nitrate aqueous solution that 90ml contains 1.50g NiO after the cooling, room temperature dipping 5 hours, 120 ℃ of dryings 6 hours, temperature programming to 540 ℃ roasting 6 hours; Put into 90ml after the cooling and contain 4.0g WO
3Ammonium metatungstate aqueous solution in, room temperature dipping 4 hours, 120 ℃ of dryings 6 hours, temperature programming to 540 ℃ roasting 4 hours made 1.0wt%La
2O
3-3.0wt%NiO-8.0wt%WO
3/ HZSM-5 composite modified catalyst.
Embodiment 6
The application of present embodiment explanation catalyst in FCC gasoline upgrading process.Catalyst makes by embodiment 3, and 2g packs in the constant temperature zone of small fixed reaction tube.Hydrogen is with mass-flow gas meter control and metering, and reaction raw materials (FCC gasoline) is with the control of micro-sampling pump, and enters beds after hydrogen mixes.Product is after gas-liquid separation, and product liquid is collected at the gas-liquid separation pot bottom, emptying after the gas dosing.Reaction condition is: 370 ℃ of temperature; Pressure 3.0MPa; Mass space velocity 3.0h
-1Hydrogen to oil volume ratio 600.Catalyst sees Table 1 to the 300h evaluation result of FCC gasoline upgrading, and the biased sample of reformulated gasoline 300h and raw material contrast see Table 2.
Table 1 catalyst is to the 300h evaluation result of FCC gasoline upgrading
| Reaction time (h) | The composition of reformulated gasoline (vol%) | Sulphur (μ g/g) | ||
| Alkene | Aromatic hydrocarbons | Saturated hydrocarbons | ||
| 24 48 84 108 156 192 240 300 | 8.0 9.4 11.2 13.6 14.9 15.3 15.7 15.9 | 42.4 40.8 40.1 39.8 39.7 39.6 39.8 39.5 | 49.6 49.8 48.7 46.6 45.4 45.1 44.5 44.6 | 101 105 121 147 177 190 196 210 |
Table 2 reformulated gasoline 300h biased sample and raw material contrast
| Project | Gasoline is formed (vol%) | Sulphur (μ g/g) | RON | ||
| Alkene | Aromatic hydrocarbons | Isoparaffin | |||
| Test method feed gasoline reformulated gasoline | GB/T 11132 32.5 13.9 | GB/T 11132 33.5 39.8 | GB/T 11132 24.1 32.7 | GB/T 17040 744 178 | GB/T 5487 94.1 93.9 |
In the 300h of FCC gasoline upgrading running, have the performance of olefin(e) centent and sulfur content in the very strong reduction gasoline by visible this catalyst of table 1, have stable aromatisation performance simultaneously.By table 2 as seen, the volume fraction of olefins of gasoline drops to 13.9% by 32.5% behind the upgrading, alkene saturation factor 57%; Sulfur content drops to 178 μ g/g, desulfurization degree 76% by 744 μ g/g; Simultaneously behind the upgrading in the gasoline high-octane aromatic hydrocarbons and isoparaffin content increase, therefore kept the octane number of gasoline substantially.
Embodiment 7
The application of present embodiment explanation catalyst aspect the coker gasoline catalytic reforming.Catalyst makes by embodiment 4, pack into the constant temperature zone of fixed bed reaction pipe of 2g catalyst.Hydrogen is with mass-flow gas meter control and metering, and coker gasoline is with the control of micro-sampling pump, and enters beds after hydrogen mixes.Product is after gas-liquid separation, and product liquid is collected at the gas-liquid separation pot bottom, emptying after the gas dosing.Reaction condition is: 400 ℃ of temperature; Pressure 3.0MPa; Mass space velocity 3.0h
-1Hydrogen to oil volume ratio 600.Catalyst the results are shown in Table 3 to coking gasoline catalyzing upgrading.
Table 3 catalyst is to the performance of coking gasoline upgrading
| Project | The coker gasoline raw material | The upgrading afterproduct |
| Alkene (vol%) aromatic hydrocarbons (vol%) isoparaffin (vol%) n-alkane (vol%) cycloalkane (vol%) sulphur (μ g/g) RON | 23.4 12.5 15.5 35.7 12.9 1856 64.8 | 13.9 22.8 39.0 14.2 10.1 257 89.7 |
By table 3 as seen, coker gasoline is behind catalytic reforming, and alkene and sulfur content descend significantly, and low-octane n-alkane significantly descends simultaneously, and high-octane aromatic hydrocarbons and isoparaffin significantly increase, so the octane number of gasoline increases substantially behind the upgrading.
Embodiment 8
The application of present embodiment explanation catalyst aspect the direct steaming gasoline catalytic reforming.Catalyst makes by embodiment 5, pack into the constant temperature zone of fixed bed reaction pipe of 2g catalyst.Hydrogen is with mass-flow gas meter control and metering, and direct steaming gasoline is with the control of micro-sampling pump, and enters beds after hydrogen mixes.Product is after gas-liquid separation, and product liquid is collected at the gas-liquid separation pot bottom, emptying after the gas dosing.Reaction condition is: 400 ℃ of temperature; Pressure 3.0MPa; Mass space velocity 3.0h
-1Hydrogen to oil volume ratio 600.Catalyst the results are shown in Table 4 to the direct steaming gasoline catalytic reforming.
Table 4 catalyst is to the performance of direct steaming gasoline upgrading
| Project | The direct steaming gasoline raw material | The upgrading afterproduct |
| Alkene (vol%) aromatic hydrocarbons (vol%) isoparaffin (vol%) n-alkane (vol%) | 0.5 3.9 29.1 39.2 | 0.3 19.1 48.6 12.8 |
| Cycloalkane (vol%) sulphur (μ g/g) RON | 27.3 140 54.8 | 19.2 27 87.4 |
By table 4 as seen, direct steaming gasoline sulfur content behind catalytic reforming drops to 27 μ g/g, desulfurization degree 81% by 140 μ g/g.Low-octane n-alkane volume fraction descends 26.4% behind the upgrading, and high-octane aromatic hydrocarbons and isoparaffin volume fraction increase by 15.2% and 19.5% respectively, so organon.
Claims (7)
1. be used for low quality light oil catalytic reforming Preparation of catalysts method, it is characterized in that, the catalyst that this preparation method uses is to be the nano-ZSM-5 molecular sieve of 60%-80%, the carrier A l of weight percentage 10%-30% by weight percentage
2O
3, the lanthanide rare metal oxide of weight percentage 1%-20% and transition metal oxide form, and floods modification in molar concentration is the citric acid of 0.1-2.0mol/L, drying, roasting are made, preparation process of the present invention is:
With weight percentage is the carrier A l of 60%-80% nano-ZSM-5 molecular sieve and weight percentage 10%-30%
2O
3Mix, adding weight percentage is the binding agent sesbania powder of 1.0%-5.0%, adds volume ratio 1%-10%HNO again
3Aqueous solution is even, extruded moulding, and temperature programming is to 500-600 ℃, roasting 3-10 hour; Putting into molar concentration after the cooling again is the 0.1-1.0mol/L aqueous ammonium nitrate solution, presses solid-to-liquid ratio (g/ml) 1-3: 10, and normal temperature dipping 2 times, each 4-8 hour, spend deionised water, nanometer HZSM-5 catalyst is made in filtration, dry, roasting; The HZSM-5 catalyst is carried out hydrothermal treatment consists modification, metal oxide-loaded modification and the modification of citric acid dipping successively, make composite modified catalyst.
2. according to the described low quality light oil catalytic reforming Preparation of catalysts method that is used for of claim 1, it is characterized in that the grain size of described nano-ZSM-5 molecular sieve is 20-100nm.
3. according to the described low quality light oil catalytic reforming Preparation of catalysts method that is used for of claim 1, it is characterized in that described lanthanide rare metal oxide is selected from La
2O
3, transition metal oxide is selected from NiO, CoO, WO
3And MoO
3In one or more.
4. according to the described low quality light oil catalytic reforming Preparation of catalysts method that is used for of claim 1, it is characterized in that described hydrothermal treatment consists modification is that nanometer HZSM-5 catalyst is put into the hydrothermal treatment consists stove, at 400-700 ℃, with air speed 0.1-1.0h
-1Fed steam treatment 2-10 hour.
5. according to the described low quality light oil catalytic reforming Preparation of catalysts method that is used for of claim 1, it is characterized in that described metal oxide-loaded modification is that the HZSM-5 catalyst is put into lanthanum nitrate aqueous solution, normal temperature dipping 4-10 hour, 90-120 ℃ of oven dry, 540 ℃ roasting 3-10 hour; Put into the nitrate or the sulfate solution of nickel or cobalt metal after the cooling, normal temperature dipping 4-10 hour, 90-120 ℃ of oven dry, 540 ℃ roasting 3-10 hour; Put into ammonium heptamolybdate or ammonium metatungstate aqueous solution after the cooling again, normal temperature dipping 4-10 hour, 90-120 ℃ of oven dry, 540 ℃ roasting 3-10 hour.
6. according to the described low quality light oil catalytic reforming Preparation of catalysts method that is used for of claim 1, it is characterized in that, the modification of described citric acid dipping is that the HZSM-5 catalyst is put into molar concentration is the 0.1-2.0mol/L aqueous citric acid solution, normal temperature dipping 4-10 hour, 90-120 ℃ of oven dry, temperature programming to 540 ℃ roasting 3-10 hour.
7. according to the described low quality light oil catalytic reforming Preparation of catalysts method that is used for of claim 1, it is characterized in that described composite modified catalyst is applied to the catalytic reforming of catalytically cracked gasoline, coker gasoline and direct steaming gasoline.
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|---|---|---|---|
| CNA2007100116898A CN101108363A (en) | 2007-06-11 | 2007-06-11 | Manufacturing method of catalyzer used for low quality light oil catalytic reforming and application thereof |
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| CN102051208A (en) * | 2010-12-23 | 2011-05-11 | 中国石油天然气股份有限公司 | Olefin hydroisomerization and thiophene sulfur removal method |
| CN102423718A (en) * | 2011-10-20 | 2012-04-25 | 中国石油大学(北京) | Preparation method for novel FCC (Fluid Catalytic Cracking) gasoline low-temperature sulfur transfer catalyst |
| CN101757944B (en) * | 2008-12-25 | 2012-05-30 | 中国石油化工股份有限公司 | Cracking additive for increasing production of liquid gas and preparation method thereof |
| CN102794195A (en) * | 2012-08-28 | 2012-11-28 | 丁泳 | Catalyst suitable for enhancing gasoline octane number of fuel and lowering olefin content and application thereof |
| CN101560406B (en) * | 2008-03-25 | 2013-02-20 | 杭州林达化工科技有限公司 | Method and device for producing hydrocarbon by Fishcer-Tropsch reaction of synthesis gas |
| CN103952242A (en) * | 2014-04-26 | 2014-07-30 | 东北农业大学 | Application of blocky non-loaded nanocrystalline nickel material in catalytic modification on pine nut shell pyrolysis bio-oil |
| CN109385305A (en) * | 2017-08-09 | 2019-02-26 | 中国石油化工股份有限公司 | A method of low-sulphur oil is produced by sulfur-bearing straight-run naphtha |
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| CN101560406B (en) * | 2008-03-25 | 2013-02-20 | 杭州林达化工科技有限公司 | Method and device for producing hydrocarbon by Fishcer-Tropsch reaction of synthesis gas |
| CN101757944B (en) * | 2008-12-25 | 2012-05-30 | 中国石油化工股份有限公司 | Cracking additive for increasing production of liquid gas and preparation method thereof |
| CN102051208B (en) * | 2010-12-23 | 2013-11-06 | 中国石油天然气股份有限公司 | Olefin hydroisomerization and thiophene sulfur removal method |
| CN102051208A (en) * | 2010-12-23 | 2011-05-11 | 中国石油天然气股份有限公司 | Olefin hydroisomerization and thiophene sulfur removal method |
| CN102423718A (en) * | 2011-10-20 | 2012-04-25 | 中国石油大学(北京) | Preparation method for novel FCC (Fluid Catalytic Cracking) gasoline low-temperature sulfur transfer catalyst |
| CN102423718B (en) * | 2011-10-20 | 2013-05-15 | 中国石油大学(北京) | Preparation method for novel FCC (Fluid Catalytic Cracking) gasoline low-temperature sulfur transfer catalyst |
| CN102794195A (en) * | 2012-08-28 | 2012-11-28 | 丁泳 | Catalyst suitable for enhancing gasoline octane number of fuel and lowering olefin content and application thereof |
| CN102794195B (en) * | 2012-08-28 | 2014-08-27 | 丁泳 | Catalyst suitable for enhancing gasoline octane number of fuel and lowering olefin content and application thereof |
| CN103952242A (en) * | 2014-04-26 | 2014-07-30 | 东北农业大学 | Application of blocky non-loaded nanocrystalline nickel material in catalytic modification on pine nut shell pyrolysis bio-oil |
| CN103952242B (en) * | 2014-04-26 | 2016-05-18 | 东北农业大学 | Block non-loaded nano-crystal nickel material is to pine nut shell pyrolysis bio oil modification application |
| CN109385305A (en) * | 2017-08-09 | 2019-02-26 | 中国石油化工股份有限公司 | A method of low-sulphur oil is produced by sulfur-bearing straight-run naphtha |
| CN109385305B (en) * | 2017-08-09 | 2022-08-09 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline from sulfur-containing straight-run naphtha |
| CN112322332A (en) * | 2020-10-21 | 2021-02-05 | 中国石油大学(北京) | Alkane-alkene co-cracking catalyst and alkane-alkene mixed catalytic cracking method |
| CN112322332B (en) * | 2020-10-21 | 2021-11-16 | 中国石油大学(北京) | Alkane-alkene co-cracking catalyst and alkane-alkene mixed catalytic cracking method |
| CN113083356A (en) * | 2021-03-31 | 2021-07-09 | 中国石油大学(北京) | Mesoporous and microporous ZSM-5/alumina catalyst and preparation method and application thereof |
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