CN1219033C - Fractional oil hydrogenation desulphurizing and deacromating process - Google Patents
Fractional oil hydrogenation desulphurizing and deacromating process Download PDFInfo
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- CN1219033C CN1219033C CN 03133551 CN03133551A CN1219033C CN 1219033 C CN1219033 C CN 1219033C CN 03133551 CN03133551 CN 03133551 CN 03133551 A CN03133551 A CN 03133551A CN 1219033 C CN1219033 C CN 1219033C
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Abstract
The present invention discloses a hydrogenating treatment method of distillate oil, particularly a two-stage hydrodesulphurization and dearomatization method of distillate oil. In the method, a two-stage hydrogenation flow is adopted, a non noble metal hydrofining catalyst is used in a first stage, a noble metal hydrogenation catalyst is used in a second stage, wherein circulating hydrogen and the distillate oil as raw materials are mixed and supplied into a first reactor to react with each other; liquid phases of separated effluents of the reactor in the first stage and new hydrogen are mixed and supplied into a second reactor to react with each other. The method has the advantage of reasonable process flow. A hydrogen source used in the first stage is different from a hydrogen source used in the second stage, and the requirement of the catalysts in both stages for the sulphur contents in the hydrogen sources is avoided so that the catalysts in both of the two stages have favorable activity stability.
Description
Technical field
The present invention relates to the method that a kind of distillate hydrogenation is handled, especially a kind of two-stage hydrogenation is handled the method that removes sulfocompound and aromatic hydrocarbons in the distillate.
Background technology
Along with world economy and developing of automobile industry, the aggregate demand of vehicle fuel grows with each passing day, and the quantity discharged of pollutent is also increasing in the vehicle exhaust, and the atmosphere polluting problem that causes is more and more serious, and people are also more and more stronger to environmental protection consciousness.Market is to the increasingly stringent that requires of petroleum products, and countries in the world have been revised fuel standard in succession.Aspects such as sulphur content, aromaticity content, density and cetane value to diesel product in new specification have all proposed stricter requirement, and particularly the requirement of sulphur content and aromaticity content is harsh more.II class diesel oil index request sulphur content is less than 300 μ g/g in " world's fuel oil standard ", and aromaticity content is less than 25wt%; III class diesel oil index request sulphur content less than 30 μ g/g, aromaticity content less than 15wt%.
With straight-run diesel oil or catalytic diesel oil is the above-mentioned new spec diesel oil of raw material production, to transform existing hydro-refining unit, promptly adopt and improve the device pressure rating, reduce reaction velocity or improve temperature of reaction and the active higher means such as catalyst for refining of replacing, so that the sulphur content in the diesel product reaches requirement, but the content that reduces aromatic hydrocarbons then is a great problem.At present, it is under the pressure rating of existing apparatus that diesel oil deep takes off the method that aromatic hydrocarbons adopts, and utilizes that the low temperature hydrogenation of noble metal catalyst is active to come saturated aromatic hydrocarbons, thereby reduces the aromaticity content in the diesel oil effectively.
US5,183,556 two-stage hydrogenations of having introduced a kind of diesel oil take off fragrant process.At first, raw material and hydrogen following current are by being equipped with first section reaction bed of non-precious metal catalyst; Then, remove by the gaseous fraction in first section logistics that obtains by gas-liquid separation device, liquid phase stream then enters second section reaction bed and the hydrogen make-up counter current contact is carried out the deep hydrogenation reaction, and this section catalyst system therefor can be a noble metal catalyst, also can be non-precious metal catalyst.Two step hydrogenation processes can be carried out in same reactor, also can carry out in two different reactors.Between first section and second section, be provided with the gas delivery district, first section and second section gas that is produced are told reactor, directly enter second section from first section liquid phase of coming out.But second section reaction of this technological process is to carry out under the situation of material and hydrogen adverse current, realizes this technological process, and be very complicated on engineering, and engineering investment cost is also very high.
CN1267709A has proposed a kind of method of distillate two-stage hydrogenation desulfurizing and dearomatizing, stock oil at first enters in first reactor, in the presence of hydrogen and non-precious metal catalyst, react, the material that reaction generates enters high pressure hot separator, the material that comes out from the high pressure hot separator bottom enters second reactor, in the presence of hydrogen and noble metal catalyst, react, after the material that reaction generates passes through high-pressure separator, light pressure separator successively, obtain liquid product, the hydrogen-rich gas at high-pressure separator top recycles.The product aromaticity content that this method obtains can drop to below the 10wt%, and yield is up to more than the 95wt%.But, the hydrogen-rich gas that contain hydrogen sulfide of this invention after through first reactor, second reactor reaction, through recycling after the desulphurization system desulfurization, satisfy in second reactor noble metal catalyst to hydrogen sulfide content requirement in the system if hydrogen sulfide content in this hydrogen-rich gas taken off, the content of hydrogen sulfide can not satisfy the interior non-precious metal catalyst of first reactor to hydrogen sulfide content requirement in the system in this recycle hydrogen so, thereby influence the activity stability of non-precious metal catalyst; Otherwise,, thereby influence the activity stability of noble metal catalyst if the hydrogen sulfide content height in the recycle hydrogen then can make noble metal catalyst poison again.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of method of distillate two-stage hydrogenation desulfurizing and dearomatizing.
The method that fraction oil hydrodesulfurizing of the present invention takes off aromatic hydrocarbons is to adopt the two-stage hydrogenation flow process, first section is used the non-noble metal hydrogenation catalyst for refining, second section is used noble metal hydrogenation catalyst, wherein recycle hydrogen and distillate feedstock are mixed into the first reactor dereaction, and the liquid phase of the effluent of first section reactor after separating is mixed into the second reactor dereaction with new hydrogen.
The concrete steps of the inventive method are as follows:
A. distillate feedstock and the hydrogen after the process furnace heating are mixed in first reactor, react in the presence of the non-noble metal hydrogenation catalyst for refining;
B. the material of first reactor generation enters high pressure hot separator, and the gaseous phase materials that comes out from the high pressure hot separator top is after the cold high pressure separator condensation goes out partially liq, and residual gas obtains hydrogen-rich gas and recycles for first reactive system through desulfurization;
C. material that comes out from the high pressure hot separator bottom and the fresh hydrogen after heat exchange are mixed into second reactor, react in the presence of noble metal hydrogenation catalyst;
D. after the material of second reactor generation passes through high-pressure separator, light pressure separator successively, obtain liquid stream, this logistics obtains final liquid product after fractionating system removes lighter hydrocarbons, and the hydrogen-rich gas at high-pressure separator top recycles for first reactive system.
Employed distillate feedstock is selected from one or more the mixture in straight-run diesel oil, catalytic diesel oil, coker gas oil, visbreaking diesel oil and the vacuum distillate among the present invention, its sulphur content is not higher than 2.5wt%, nitrogen content is not higher than 1000 μ g/g, aromaticity content is not higher than 66wt%, and heavy metal content is not higher than 2 μ g/g.
First section used non-noble metal hydrogenation catalyst for refining is the Hydrobon catalyst of any routine, and its reactive metal preferably is selected from the cobalt of the molybdenum of group vib and tungsten and group VIII and in the nickel one or more, as Ni-Mo, Co-Mo, W-Co etc.Heat-resistant inorganic oxide as carrier is aluminum oxide, contains the aluminum oxide of boron, silicon and/or phosphorus, is preferably the aluminum oxide that contains silicon and phosphorus.
First section reaction conditions is conventional hydrofining operational condition, and be preferably: hydrogen dividing potential drop 1.8～10.0MPa is preferably 4.0～8.0MPa; Volume space velocity 0.5～6.5h
-1, be preferably 1.0～4.0h
-1280～385 ℃ of temperature of reaction are preferably 300～360 ℃; Hydrogen to oil volume ratio 100～600 is preferably 200～400.
Second section used, and to pass through metal catalyst be that a kind of loading on passed through the metal hydrogenation catalyst for refining on the zeolite, and its reactive metal is platinum and/or palladium, and zeolite is generally Y zeolite or through the Y zeolite of modification.
Second section reaction conditions is: hydrogen dividing potential drop 1.8～10.0MPa is preferably 4.0～8.0MPa; Volume space velocity 0.5～4.5h
-1, be preferably 1.0～3.0h
-1240～370 ℃ of temperature of reaction are preferably 280～350 ℃; Hydrogen to oil volume ratio 200～800 is preferably 400～600.
Described high pressure hot separator service temperature is 150～450 ℃, and the cold high pressure separator service temperature is 20～80 ℃.First reactor and second reactor are fixed bed.
Compared with prior art, method technical process of the present invention is reasonable, and first section different with second section used hydrogen source, avoided the requirement of each section inner catalyst to sulphur content in the hydrogen source, thereby makes the catalyzer in two sections all have good activity stability.
Description of drawings
Accompanying drawing is the process flow diagram of distillate two-stage hydrogenation desulfurizing and dearomatizing method provided by the invention.
1. stock oils among the figure, 2. fresh hydrogen, 3. first reactor, 4. first high pressure hot separator, 5. second reactor, 6. second high pressure hot separator; 7. first cold high pressure separator, 8. fractionating system, 9. process furnace, 10. second cold high pressure separator, 11. desulfurizers, 12. recycle compressors.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention is further specified.
Stock oil 1 pressurizes after after the heat-exchange system heat exchange through raw oil pump, enter first reactor 3, resultant of reaction enters first high pressure hot separator 4 through after the heat exchange, the liquid phase material that comes out from first high pressure hot separator 4 bottoms is after heat exchange, enter in second reactor 5, resultant of reaction is after two interchanger heat exchange, enter second high-pressure separator 6, isolated liquid phase material enters first light pressure separator 7, the liquid reacting product that obtains through separation, after the interchanger heat exchange, go fractionating system 8 again.
2 fens two-way of fresh hydrogen enter system, and the first via is divided into two branch roads again, and a branch road is as the additional cold hydrogen of first reactor 3, and another branch road enters process furnace 9 after the interchanger heat exchange, enter first reactor 3 through pipeline again; The second the tunnel is divided into two branch roads again, and wherein a branch road also has a branch road to go 5 reactions of second reactor from reactor head again after the interchanger heat exchange as the additional cold hydrogen of second reactor 5.
The gas at second high-pressure separator 6 top, enter first high pressure hot separator 4 and recommend matter as gas, the gaseous phase materials at first high pressure hot separator 4 tops is after the interchanger heat exchange, enter second cold high pressure separator 10, after gas-liquid separation, the liquid phase stream of second cold high pressure separator 10 bottom enters second light pressure separator 7, after the gas at second cold high pressure separator 10 top enters desulfurizer 11 and removes hydrogen sulfide, after the hydrogen-rich gas that obtains enters recycle compressor 12 superchargings, use for first reactor 3 as the recycle hydrogen of system.
Employed non-noble metal hydrogenation catalyst for refining in first reactor, preferably adopt a kind of on the alumina supporter of siliceous and phosphorus the catalyzer of supported active metal component, weight with catalyzer is benchmark, its active ingredient composed as follows: 10%～35% molybdenum oxide or Tungsten oxide 99.999,2.0%～6.0% nickel oxide or cobalt oxide, 2.0～6.0% P (in the P element).This siliceous and alumina supporter phosphorus is siliceously to be mixed with macroporous aluminium oxide phosphorus with a kind of by one or more little porous aluminum oxides, and the specific surface of wherein little porous aluminum oxide is 200～300m
2/ g, pore volume is 0.3～0.6ml/g, the aperture is between 2.0～10.0nm; Macroporous aluminium oxide is siliceous with SiO
2Count 1.0～4.0wt%, phosphorous with P
2O
5Count 1.0～4.0wt%, its specific surface is 400～450m
2/ g, pore volume is 0.8～1.3ml/g, the aperture is between 6.0～13.0nm.In the weight of catalyzer, macroporous aluminium oxide accounts for 30～60%, and little porous aluminum oxide accounts for 10～35%.The specific surface area of used non-precious metal catalyst is at 160～190m
2/ g, pore volume is between 0.3～0.4ml/g.This catalyzer has higher desulfurization, nitrogen removal performance, and its concrete preparation method can be with reference to CN1048037C.Adopt this non-precious metal catalyst to make oil product after reactions such as first section desulfurization, denitrogenation and polycyclic aromatic hydrocarbons that carries out distillate is saturated, the sulphur content of first section export oil drops to below the 400 μ g/g, nitrogen content drops to below the 30 μ g/g, and the aromatic hydrocarbons saturation exponent more than two rings is greater than 66%.
Employed noble metal catalyst preferably adopts following noble metal catalyst in second reactor, and its active ingredient is platinum and/or palladium.This noble metal catalyst comprises the precious metal of 0.05wt%～2.0wt%, the base metal of 0.5wt%～10.0wt%, and the Y zeolite of 58.0wt%～94.0wt% and the tackiness agent of 5.0wt%～30.0wt%, its surface-area is at 350～700m
2Between/the g, pore volume is between 0.35～0.50ml/g.This catalyzer prepares by the following method: be raw material with the Y zeolite, carry out ion-exchange with non-noble metal water soluble salt, the washing after drying carries out hydrothermal treatment consists then.Ammonium ion exchange, pickling, filtration are washed to such an extent that contain non-noble metal modified Y zeolite.Add mix behind tackiness agent, the extrusion aid pinch, roll, extruded moulding, drying, roasting obtains containing the carrier of modified Y zeolite.Carrier with the water-soluble solution dipping preparation that contains precious metal.Catalyzer behind the dipping at room temperature dries naturally, and drying, roasting obtain the catalyzer finished product then.This catalyzer has the saturated performance of higher aromatic hydrogenation, has higher desulfurization, nitrogen removal performance simultaneously, and its detailed preparation method can be with reference to CN1362490A.Adopt this catalyzer can make oil product second section further remove aromatic hydrocarbons after, the sulphur content of export oil drops to below the 30 μ g/g, aromaticity content drops to below the 10wt%, even can reach below the 5wt%.
The preferred method of the present invention compared with prior art has the following advantages:
1, use above-mentioned non-precious metal catalyst owing to first section, the sulfocompound decreasing ratio height of distillate feedstock, the sulphur content of product can drop to below the 30 μ g/g;
2, use above-mentioned noble metal catalyst owing to second section, the arene engaging scraping rate height of distillate feedstock, the aromaticity content of product can drop to aromaticity content and drop to below the 10wt%, even can reach below the 5wt%;
3, purpose product innovation yield is up to more than the 96wt%.
The following examples will be further specified the inventive method, but not thereby limiting the invention.
Below among each embodiment the composition and the physico-chemical property thereof of the employed non-precious metal catalyst of first reactor see Table 1, the character of various distillate feedstocks sees Table 2, processing condition and test-results thereof among each embodiment see Table 3.The aromaticity content of oil product adopts liquid petroleum product hydro carbons assay method (fluorescent indicator adsorption method) to measure.
Embodiment 1
With straight-run diesel oil is distillate feedstock, distillate enters in first reactor, in the presence of hydrogen and non-precious metal catalyst C-1, react, the material that reaction generates enters high pressure hot separator, the gaseous phase materials that comes out from the high pressure hot separator top is after the cold high pressure separator condensation goes out partially liq, residual gas obtains hydrogen-rich gas and recycles for first reactive system through desulfurization; The material that comes out from the high pressure hot separator bottom enters second reactor, in the presence of fresh hydrogen and palladium-containing catalyst, react, after the material that reaction generates separates through high-pressure separator, light pressure separator successively, obtain liquid product and go out device, the hydrogen-rich gas at high-pressure separator top recycles for first reactive system.
The detailed preparation method of employed palladium-containing catalyst can be with reference to the embodiment 2 of CN1362490A in second reactor.The catalyzer of preparing is CC-1, is benchmark with the weight of catalyzer, and it is composed as follows: Pd0.29%, CoO7.21%, modified Y zeolite 70%; Its character is as follows: specific surface is 568m
2/ g, pore volume are 0.404ml/g.
As can be seen from the test results, second section exported product aromaticity content is 3.9wt%.
By the technical process of above embodiment 1, the used non-precious metal catalyst of first reactor is C-2, and the used noble metal catalyst of second reactor is CC-1, changes corresponding processing parameter, has obtained effect preferably.
As can be seen from the test results, second section exported product aromaticity content is 4.3wt%.
Embodiment 3
Mixing oil with straight-run diesel oil and catalytic diesel oil is a distillate feedstock, distillate enters in first reactor, in the presence of hydrogen and non-precious metal catalyst C-3, react, the material that reaction generates enters high pressure hot separator, the gaseous phase materials that comes out from the high pressure hot separator top is after the cold high pressure separator condensation goes out partially liq, residual gas obtains hydrogen-rich gas and recycles for first reactive system through desulfurization; The material that comes out from the high pressure hot separator bottom enters second reactor, in the presence of fresh hydrogen and palladium-containing catalyst, react, after the material that reaction generates separates through high-pressure separator, light pressure separator successively, obtain liquid product and go out device, the hydrogen-rich gas at high-pressure separator top recycles for first reactive system.
The detailed preparation method of the catalyzer of nickeliferous in second reactor-palladium can be with reference to the embodiment 5 of CN1362490A.The catalyzer of preparing is CC-2, is benchmark with the weight of catalyzer, and it is composed as follows: Pd 1.16%, and NiO 2.80%, modified Y zeolite 80%; Its character is as follows: specific surface is 348m
2/ g, pore volume are 0.335ml/g.
By test-results as can be seen, second section exported product aromaticity content is 3.1wt%.
By the technical process of above embodiment 3, the used non-precious metal catalyst of first reactor is C-4, and the used noble metal catalyst of second reactor is CC-2, changes corresponding processing parameter, has obtained better effects.
By test-results as can be seen, second section exported product aromaticity content is 4.8wt%.
Table 1 catalyzer physico-chemical property
| The catalyzer numbering | C-1 | C-2 | C-3 | C-4 |
| Form wt% | - | - | - | - |
| MoO 3 | 24 | 30 | 13 | - |
| WO 3 | - | - | - | 33 |
| NiO | 4.5 | 3.0 | 6.0 | - |
| CoO | - | - | - | 2.5 |
| SiO 2 | 1.6 | 3.0 | 2.0 | 4.0 |
| P | 2.4 | 4.3 | 1.7 | 3.0 |
| Al 2O 3 | Surplus | Surplus | Surplus | Surplus |
| Specific surface area, m 2/g | 178 | 162 | 190 | 170 |
| Pore volume, ml/g | 0.338 | 0.333 | 0.348 | 0.335 |
Table 2 stock oil character
| Analysis project | Straight-run diesel oil | The mixing oil of straight-run diesel oil and catalytic diesel oil |
| Density, g/cm 3(20℃) | 0.8789 | 0.8825 |
| Boiling range, IBP/EBP, ℃ (ASTM-D1160) | 196/357 | 186/381 |
| S，μg/g | 1322 | 1255 |
| N，μg/g | 735 | 905 |
| Aromatic hydrocarbons, wt% | 54.5 | 46.3 |
| Carbon residue, wt% | 0.06 | 0.25 |
| Condensation point, ℃ | -3 | -8 |
Table 3 catalyzer distillate hydrogenation reaction evaluating result
| Numbering | Example 1 | Example 2 | Example 3 | Example 4 | ||||
| Reactor | One is anti- | Two is anti- | One is anti- | Two is anti- | One is anti- | Two is anti- | One is anti- | Two is anti- |
| The catalyzer numbering | C-1 | CC-1 | C-2 | CC-1 | C-3 | CC-2 | C-4 | CC-2 |
| Reaction conditions | ||||||||
| The hydrogen dividing potential drop, MPa | 6.4 | 6.4 | 8.0 | 8.0 | 4.0 | 4.0 | 10.0 | 10.0 |
| Hydrogen to oil volume ratio | 800 | 800 | 600 | 600 | 800 | 800 | 600 | 600 |
| Volume space velocity, h -1 | 2.0 | 2.0 | 4.0 | 1.2 | 1.2 | 1.0 | 1.0 | 3.0 |
| Temperature of reaction, ℃ | 370 | 330 | 385 | 288 | 330 | 280 | 355 | 345 |
| Generate fluid body yield, wt% | 96.2 | 96.0 | 96.4 | 96.1 | ||||
| Generate oil nature | ||||||||
| S，μg/g | 13.0 | 10.9 | 14.3 | 9.7 | ||||
| Aromatic hydrocarbons, wt% | 3.9 | 4.3 | 3.1 | 4.8 | ||||
| Aromatics conversion rate, wt% | 92.8 | 92.1 | 94.3 | 91.2 | ||||
Claims (9)
1, a kind of fraction oil hydrodesulfurizing takes off the method for aromatic hydrocarbons, adopt the two-stage hydrogenation flow process, first section is used the non-noble metal hydrogenation catalyst for refining, second section is used noble metal hydrogenation catalyst, it is characterized in that recycle hydrogen and distillate feedstock are mixed into the first reactor dereaction, the liquid phase of the effluent of first section reactor after separating is mixed into the second reactor dereaction with new hydrogen.
2, take off the method for aromatic hydrocarbons according to the fraction oil hydrodesulfurizing of claim 1, it is characterized in that described non-noble metal hydrogenation catalyst for refining is is carrier with siliceous and aluminum oxide phosphorus, with catalyst weight per-cent is benchmark, its active ingredient and composed as follows: 10%～35% molybdenum oxide or Tungsten oxide 99.999,2.0%～6.0% nickel oxide or cobalt oxide, in the P element, 2.0%～6.0% P.
3, take off the method for aromatic hydrocarbons according to the fraction oil hydrodesulfurizing of claim 1 or 2, the specific surface area that it is characterized in that described non-noble metal hydrogenation catalyst for refining is at 160～190m
2/ g, pore volume is between 0.3～0.4ml/g.
4, take off the method for aromatic hydrocarbons according to the fraction oil hydrodesulfurizing of claim 1, it is characterized in that described noble metal hydrogenation catalyst, with catalyst weight per-cent is benchmark, comprise 0.05%～2.0% precious metal, 0.5%～10.0% base metal, 58.0%～94.0% Y zeolite and 5.0%～30.0% tackiness agent.
5, the method for taking off aromatic hydrocarbons according to claim 1 or 4 described fraction oil hydrodesulfurizings, the surface-area that it is characterized in that described noble metal hydrogenation catalyst is at 350～700m
2Between/the g, pore volume is between 0.35～0.50ml/g.
6, fraction oil hydrodesulfurizing according to claim 1 takes off the method for aromatic hydrocarbons, it is characterized in that described first section reaction conditions is:
Hydrogen dividing potential drop: 1.8～10.0MPa;
Volume space velocity: 0.5～6.5h
-1
Temperature of reaction: 280～385 ℃;
Hydrogen to oil volume ratio: 100～600.
7, fraction oil hydrodesulfurizing according to claim 1 takes off the method for aromatic hydrocarbons, it is characterized in that described first section reaction conditions is:
Hydrogen dividing potential drop: 4.0～8.0MPa;
Volume space velocity: 1.0～4.0h
-1
Temperature of reaction: 300～360 ℃;
Hydrogen to oil volume ratio: 200～400.
8, fraction oil hydrodesulfurizing according to claim 1 takes off the method for aromatic hydrocarbons, it is characterized in that described second section reaction conditions is:
Hydrogen dividing potential drop: 1.8～10.0MPa;
Volume space velocity: 0.5～4.5h
-1
Temperature of reaction: 240～370 ℃;
Hydrogen to oil volume ratio: 200～800.
9, fraction oil hydrodesulfurizing according to claim 1 takes off the method for aromatic hydrocarbons, it is characterized in that described second section reaction conditions is:
Hydrogen dividing potential drop: 4.0～8.0MPa;
Volume space velocity: 1.0～3.0h
-1
Temperature of reaction: 280～350 ℃;
Hydrogen to oil volume ratio: 400～600.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549357A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Precious metal hydrogenation catalyst, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724459B (en) * | 2008-10-31 | 2012-12-12 | 中国石油化工股份有限公司 | Hydrogenation method for reducing condensation point of diesel oil |
| CN102115678B (en) * | 2010-01-06 | 2014-05-21 | 中国石油化工集团公司 | Hydrogenation and desulfurization method of diesel oil and device thereof |
| CN102115679B (en) * | 2010-01-06 | 2014-03-19 | 中国石油化工集团公司 | Method and device for producing low-sulfur diesel |
| CN103059974B (en) * | 2011-10-18 | 2015-05-20 | 中国石油化工股份有限公司 | Hydrotreatment method for producing food grade solvent naphtha |
| WO2013067323A1 (en) * | 2011-11-04 | 2013-05-10 | Saudi Arabian Oil Company | Hydrotreating and aromatic saturation process with integral intermediate hydrogen separation and purification |
| CN110465304A (en) * | 2019-08-28 | 2019-11-19 | 辽宁科技大学 | A kind of preparation method of high activity hydrogenation and desulphurization catalyst |
| CN110465305B (en) * | 2019-08-28 | 2022-10-04 | 辽宁科技大学 | Preparation method of acidic supported hydrodesulfurization catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104549357A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Precious metal hydrogenation catalyst, preparation method and application thereof |
| CN104549357B (en) * | 2013-10-23 | 2017-03-22 | 中国石油化工股份有限公司 | Precious metal hydrogenation catalyst, preparation method and application thereof |
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