CN1205310C - Hydrocarbon desulfurizing adsorbent - Google Patents
Hydrocarbon desulfurizing adsorbent Download PDFInfo
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- CN1205310C CN1205310C CN 02144948 CN02144948A CN1205310C CN 1205310 C CN1205310 C CN 1205310C CN 02144948 CN02144948 CN 02144948 CN 02144948 A CN02144948 A CN 02144948A CN 1205310 C CN1205310 C CN 1205310C
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Abstract
The present invention discloses a desulfurizing adsorbent for removing sulphide contained in hydrocarbon. The present inveniton comprises titanium dioxide, aluminium oxide, silicon dioxide and a nickel and molybdenum bimetallic component. The desulfurizing adsorbent uses the titanium oxide having high adsorption on the sulfide, a desulfurizing rate is high, and gasoline (organic sulfur content is not larger than 100 mug/g) with high sulfur content can be processed. The present invention has the advantages of no precious metal and low price. Organic sulfide and hydrogen sulphide in the hydrocarbon can be removed under the conditions of low temperature and non-contiguous hydrogen so that the sulfur content of the desulfurizing gasoline is smaller than 0.2 mug/g. The present invention is suitable for desulfurizing the gasoline, hydrocarbon gas, hydrogen and the mixed gas of the hydrogen and the hydrocarbon and is particularly suitable for the gasoline raw material desulphurization of a gasoline fuel battery system.
Description
Technical field
The present invention relates to a kind of hydro carbons refining desulfurization sorbent material and preparation method thereof, particularly a kind of gasoline non-hydrogen desulfurization sorbent material and preparation method thereof.
Background technology
At present, along with the strictness of environmental regulation, to the increasingly stringent that requires of refinery gas and sulfur in gasoline content; In addition, fuel cell and fuel cell car efficient, clean, low noise cause people's attention just day by day as a kind of new Energy utilization patterns, but the Fuel Petroleum battery car wants commercialization must solve the problem of gasoline with car hydrogen manufacturing and gasoline desulfur.
Non-leaded gasoline hydrogen manufacturing is at present used the lower nickel-containing catalyst of low temperature hydrogen production activity, the service temperature of device higher (about 800 ℃) usually.So high service temperature is feasible in factory, but is used for the Fuel Petroleum battery car, obviously is difficult to realize, and exists a lot of dangerous.
In order to reduce the temperature of reaction of gasoline steam reforming hydrogen manufacturing, there is patent WO 9948805 to propose to use precious metal (platinum, palladium, rhodium or ruthenium) catalyzer, temperature of reaction can be reduced to 400-650 ℃.But noble metal catalyst is very responsive to sulphur, and sulphur very easily makes the noble metal component on the catalyzer poison in the stock oil, therefore the stock oil sulphur content is required very strictness, and general requirement is not more than 0.2 μ g/g.General gasoline products does not all reach so low sulphur content, has limited it so greatly and has selected the scope of stock oil for use; In addition, sulphur content has fluctuation will the activity of catalyst for preparing hydrogen be exerted an influence slightly in the stock oil.
U.S. Xue Fulong company (US 4163708) has developed a kind of gasoline liquid phase Adsorption Desulfurization protection bed technique at catalytic reforming raw material oil, and has developed the cupric desulfuration adsorbent, and its carrier mainly is to adopt aluminum oxide and silicon oxide.The sulfur capacity of this desulfuration adsorbent is low, is further improved.
US 4336130 and US 4419224 have developed nickel-molybdenum-platinum type sweetening agent and the nickel-platinum type sweetening agent that sulfur capacity is higher than the copper sweetening agent, the sulphur content of catalytic reforming gasoline can be taken off to being lower than 0.5 μ g/g under higher space velocity.Though these two kinds are used the gasoline liquid phase Adsorption Desulfurization protection bed technique sweetening effectiveness of precious metal sweetening agent better, owing to use precious metal, price comparison costliness.
CN 86100015A discloses a kind of hydro carbons low temperature liquid phase sweetening agent, and this sweetening agent uses the nickel metal component, is carrier with diatomite, silicon-dioxide and aluminium sesquioxide, is the convergent improvement agent with sesbania powder, organic acid, mineral acid and tensio-active agent.The desulfurization degree and the sulfur capacity of this desulfuration adsorbent are lower, can not be used for the higher gasoline of organic sulfide removal content.
Technology contents
The purpose of this invention is to provide a kind of base metal desulfuration adsorbent and preparation method thereof, the ability of the sulfur capacity height of this sorbent material, absorption inorganic sulfur and organosulfur is strong, is specially adapted to remove the organic sulfide in the gasoline.
Desulfuration adsorbent of the present invention comprises titanium dioxide, aluminium sesquioxide, silicon-dioxide and nickel, molybdenum bimetal component.Weight with sorbent material is benchmark, and content of titanium dioxide is 10～50%, with 15～40% for well; Aluminium sesquioxide content is 5～40%, with 10～30% for well; Dioxide-containing silica is 0～20%, with 5～10% for well; Nickel content in NiO is 20～50%, with 30～40% for well; With MoO
3The molybdenum content of meter is 10～40%, with 15～25% for well.
Concrete when implementing method of the present invention, described desulfuration adsorbent specific surface area is 20～200m
2/ g, pore volume are 0.3～0.5ml/g, can several apertures be 6～20nm.
Desulfuration adsorbent of the present invention is to adopt the kneading method preparation, its step is as follows: (1) mixes hydrated aluminum oxide, titanium oxide powder, silicon-dioxide or silicon-containing compound and the extrusion aid (sesbania powder or citric acid) of metering or compound the extrusion aid mixture of citric acid (the sesbania powder with), preferably uses compound extrusion aid.The nitric acid of adding metering or acetic acid solution, water are mediated then.The molybdate compound, the nickel compound containing that add metering in the kneading process are again mediated to being plastic shape; (2) extruded moulding, its shape is determined by orifice plate; (3) the wet bar after the moulding was at 105-130 ℃ of dry 4-8 hour; Place High Temperature Furnaces Heating Apparatus, roasting 6-10 hour, maturing temperature was 550-750 ℃, was preferably 600-700 ℃; (4) cartridge reactor of packing into feeds hydrogen reducing; (5) draw off, seal up for safekeeping standby.
Titanium oxide powder can select that foreign matter content is lower for use, titanium oxide content is greater than the titanium dioxide of 98.5wt%; Also can select the lower titanium dioxide of titanium oxide content for use, the titanium oxide powder that obtains through acid treatment, hydrolysis, washing, drying, pulverizing.Preferably select the lower titanium dioxide of titanium oxide content for use, get titanium oxide after acid treatment that employing is commonly used and the hydrolysis treatment, being washed with water to the pH value is 6.5～7.5, and drying is 6～10 hours under 100～120 ℃, and crushing screening is got less than 150 purpose powders.
Hydrated aluminum oxide can adopt any suitable commercially available prod, comprises a water aluminum oxide and an alumina trihydrate.(pseudo-boehmite, molecular formula are Al to a preferred water aluminum oxide
2O
3H
2O), comprise the pseudo-boehmite that aluminum chloride and ammoniacal liquor high temperature continuous precipitation are produced, in sodium metaaluminate and the nitric acid and the pseudo-boehmite of the pseudo-boehmite of producing and Tai-Ace S 150 and aluminate continuous precipitation production.
Silicon-dioxide or silicon-containing compound comprise hydrolysis oxidation silicon, diatomite, silica gel or silicon-containing compounds such as ammonium silicate, silicic acid.Preferred dioxide-containing silica is greater than the commercially available diatomite of 85wt%.
Molybdate compound is selected from molybdic oxide, ammonium molybdate, ammonium paramolybdate, Ammonium Heptamolybdate, poly ammonium molybdate or other contains molybdenum salt, preferably selects Ammonium Heptamolybdate for use.
Nickel compound containing is selected from nickelous nitrate, nickel oxide, basic nickel carbonate, nickelous chloride, nickelous acetate, nickelous oxalate or other nickeliferous metal-salt, preferably selects nickelous nitrate for use.
Described compound extrusion aid is the mixture of sesbania powder and citric acid, and sesbania powder content 40～80% is preferably 50～70%; Citric acid content 20～60% is preferably 30～50%.The add-on of extrusion aid or compound extrusion aid is 3～7% (are benchmark with the adsorbent weight), is preferably 4～6%.
The reductive condition of desulfuration adsorbent of the present invention is: hydrogen purity is not less than 80v%, and oxygen level is not more than 0.5v% in the hydrogen, 300～400 ℃ of temperature, time 5～20h, gas agent volume ratio 100～1000.
When this desulfuration adsorbent is used for the desulfurization of raw material of Fuel Petroleum battery, 100～200 ℃ of low-temp desulfurization device bed temperatures, pressure 0.5～3MPa, feed volume air speed 1～20h
-1
The prepared desulfuration adsorbent of the inventive method is not only applicable to the desulfurization of raw material of Fuel Petroleum battery system, comprise the gasoline of explained hereafter such as process pretreated straight-run spirit of hydrogenation or catalytic reforming, hydrocracking, catalytic cracking, coking, organic sulfur content can relax to 100 μ g/g in the gasoline; Also can be used for the desulfurization of hydrocarbon gas, hydrogen and hydrogen and hydro carbons mixed gas.But the adsorption desulfurize when being specially adapted to straight-run spirit as the fuel cell system charging can take off the sulphur content of gasoline to less than 0.2 μ g/g.
Has following advantage according to the resulting desulfuration adsorbent of the inventive method: because titanium oxide has stronger adsorptive power to sulphur, therefore add titanium oxide in the sorbent material, strengthened the adsorptive power of sorbent material greatly, the desulfurization degree of sorbent material and sulfur capacity height to sulfide; Use base metal, low price; Preparation process is simple; The interior jumbo fluctuation of sulphur content short period of time can not exert an influence to sweetening effectiveness in the stock oil.
Embodiment
For further specifying all main points of the present invention, enumerate following examples.
Said desulfuration adsorbent running terminal point is meant that sulphur content rises in the sweet oil through long-time running in the example, reaches the 20wt% of stock oil sulphur content.The sulphur content of stock oil and sweet oil is all analyzed with the microcoulomb method.The sulfur capacity of desulfuration adsorbent is in the hydrogen sulfide and the organosulfur weight per-cent that accounts for sweetening agent weight of absorption.
Embodiment 1
Taking by weighing titanium oxide content is titanium dioxide 500 grams of 98wt%, add deionized water 750 grams, the salpeter solution 60ml that adds 65wt% carries out acidification, after mixing, under stirring condition, adding 3N ammonia soln to pH value is 7.0, after heavyization 10 hours, with deionized water wash 2～3 times, regulating the pH value with ammonia soln again is 7.0 after-filtration, drying is 8 hours under 110 ℃, crushing screening is got less than 150 purpose titanium oxide powders, 60 grams, pseudo-boehmite 94.1 grams, diatomite (wherein silica comprises 85wt%) 60 grams are put into kneading machine, add the compound extrusion aid of the 20 grams (mixture of sesbania powder and citric acid, wherein the weight of sesbania powder accounts for 40%), add (NH
4)
6Mo
7O
244H
2O687.0 gram, Ni (NO
3)
26H
2O467.0 restrains, and adds salpeter solution 250ml and the 200ml water of 3wt% again, fully mediates; Be kneaded into extruded moulding behind the plastic.Spend the night the back 120 ℃ of dryings 6 hours at air drying; Place High Temperature Furnaces Heating Apparatus again, in 650 ℃ of roastings 10 hours.Obtain MoO
3The desulfuration adsorbent of content 20wt%, NiO content 30wt%.Its specific surface area is 180m
2/ g, pore volume are 0.46ml/g, can several apertures be 10nm.The internal diameter of packing into is 10 millimeters a cartridge reactor, feeds the hydrogen reducing of hydrogen purity 80v% (all the other 20v% are nitrogen), gas agent volume ratio 1000: 1,350 ℃ of reduction temperatures, 20 hours recovery times.Draw off, seal up for safekeeping standby.Sample number into spectrum ABS1#.
Embodiment 2
Get restraining and putting into kneading machine as the preparation of embodiment 1 method less than 150 purpose titanium oxide powders, 120 grams, pseudo-boehmite 43 grams, diatomite (wherein silica comprises 85wt%) 23.5, add the compound extrusion aid of the 16 grams (mixture of sesbania powder and citric acid, wherein the weight of sesbania powder accounts for 60%), add (NH
4)
6Mo
7O
244H
2O515.2 gram, Ni (NO
3)
26H
2O622.7 restrains, and adds acetic acid solution 280ml and the 200ml water of 5wt% again, fully mediates; Be kneaded into extruded moulding behind the plastic.Spend the night the back 120 ℃ of dryings 6 hours at air drying; Place High Temperature Furnaces Heating Apparatus again, in 650 ℃ of roastings 10 hours.Obtain MoO
3The desulfuration adsorbent of content 15wt%, NiO content 40wt%.Its specific surface area is 160m
2/ g, pore volume are 0.43ml/g, can several apertures be 12nm.The internal diameter of packing into is 10 millimeters a cartridge reactor, feeds the hydrogen reducing of hydrogen purity 95v% (all the other 5v% are nitrogen), gas agent volume ratio 100: 1,300 ℃ of reduction temperatures, 10 hours recovery times.Draw off, seal up for safekeeping standby.Sample number into spectrum ABS2#.
Embodiment 3
Get restraining and putting into kneading machine as the preparation of embodiment 1 method less than 150 purpose titanium oxide powders, 156.5 grams, pseudo-boehmite 47 grams, diatomite (wherein silica comprises 85wt%) 23.5, add the compound extrusion aid of the 18 grams (mixture of sesbania powder and citric acid, wherein the weight of sesbania powder accounts for 60%), ammonium molybdate (NH
4)
6Mo
7O
244H
2O276.7 gram, basic nickel carbonate NiCO
32Ni (OH)
24H
2O705.1 restrains, and adds salpeter solution 280ml and the 200ml water of 3wt% again, fully mediates; Be kneaded into extruded moulding behind the plastic.Spend the night the back 120 ℃ of dryings 6 hours at air drying; Place High Temperature Furnaces Heating Apparatus again, in 650 ℃ of roastings 10 hours.Obtain MoO
3The desulfuration adsorbent of content 15%, NiO content 30% (weight), its specific surface area are 155m
2/ g, pore volume are 0.40ml/g, can several apertures be 11.5nm.The internal diameter of packing into is 10 millimeters a cartridge reactor, feeds the hydrogen reducing of hydrogen purity 90v% (all the other 10v% are nitrogen), gas agent volume ratio 500: 1,400 ℃ of reduction temperatures, 5 hours recovery times.Draw off, seal up for safekeeping standby.Sample number into spectrum ABS3#.
Embodiment 4
Get restraining and putting into kneading machine as the preparation of embodiment 1 method less than 150 purpose titanium oxide powders, 80 grams, pseudo-boehmite 90.0 grams, diatomite (wherein silica comprises 85wt%) 23.5, add the compound extrusion aid of the 18 grams (mixture of sesbania powder and citric acid, wherein the weight of sesbania powder accounts for 80%), add molybdic oxide MoO
3100 grams, nickelous acetate NiCO
42H
2O274.2 restrains, and adds salpeter solution 280ml and the 200ml water of 3wt% again, fully mediates; Be kneaded into extruded moulding behind the plastic.Spend the night the back 120 ℃ of dryings 6 hours at air drying; Place High Temperature Furnaces Heating Apparatus again, in 650 ℃ of roastings 10 hours.Obtain MoO
3The desulfuration adsorbent of content 25wt%, NiO content 30wt%, its specific surface area are 190m
2/ g, pore volume are 0.49ml/g, can several apertures be 10.5nm.The internal diameter of packing into is 10 millimeters a cartridge reactor, feeds the hydrogen reducing of hydrogen purity 90v% (all the other 10v% are nitrogen), gas agent volume ratio 800: 1,350 ℃ of reduction temperatures, 10 hours recovery times.Draw off, seal up for safekeeping standby, sample number into spectrum ABS4#.
Embodiment 5～7
Test oil is the straight-run spirit of 60～170 ℃ of boiling ranges, and this oil separates and stripping through hydrofining, low pressure, and organic sulfur content is less than 0.5 μ g/g.Add hexylmercaptan in stock oil, organic sulfur content is respectively test oil 1#, 2#, the 3# of 10,50,100 μ g/g in making up oil.
The sweetening agent sample ABS1#100ml that the embodiment 1 that packs in tubular reactor prepares, bed temperature rises to 120 ℃.
With 2.0h
-1Air speed (v) successively feed test oil 1#, 2#, the 3# that organic sulfur content is respectively 10,50,100 μ g/g.Through 300 hours running, the sulphur content of sweet oil was all less than 0.2 μ g/g.The sulfur capacity of running terminal point desulfuration adsorbent is 25%.
The result of embodiment 5～7 shows, is not more than the gasoline of 100 μ g/g for organic sulfur content, and sweetening agent of the present invention all can take off sulphur content to less than 0.2 μ g/g, and desulfurization degree is higher.
Embodiment 8～10
Test oil is the straight-run spirit after refining (same with embodiment 5～7 raw materials used oil phases).In test oil, add n-butyl mercaptan, prepare two kinds of stock oils.A kind of is normal test oil 4#, sulphur content 10 μ g/g in the oil, and another is the test oil 5# of sulphur content 150 μ g/g.Normal process of the test adopts the test oil 4# of sulphur content 10 μ g/g, and the test oil 5# of short period of time (10 minutes) feed sulphur content 150 μ g/g recovers test oil 4# afterwards, investigates the influence of interior stock oil sulphur content unusual fluctuations sweetening agent of short period of time and sweetening effectiveness.Adopt the sweetening agent ABS2# of embodiment 2 preparations.Test-results sees Table 1.
The unusual fluctuations of table 1 stock oil sulphur content are to the influence of sweetening effectiveness
| Embodiment | 8 | 9 | 10 |
| Time | Before the sulphur content fluctuation | In the sulphur content wave process | After the sulphur content fluctuation stops 200 hours |
| Stock oil | 4# | 5# | 4# |
| Stock oil sulphur content/μ g/g | 10 | 150 | 10 |
| Bed temperature/℃ | 120 | 120 | 120 |
| Sweet oil sulphur content/μ g/g | ＜0.2 | ＜0.2 | ＜0.2 |
The result of embodiment 8～10 shows, the unusual fluctuations of stock oil sulphur content illustrate that to not influence of sweetening effectiveness low-temp desulfurization agent of the present invention can play the effect of protection downstream precious metal catalyst for preparing hydrogen in the short period of time.
Embodiment 11
Test oil is the straight-run spirit after refining (same with embodiment 5～7 raw materials used oil phases).In stock oil, charge into hydrogen sulfide, make its rate and inorganic sulphur content increase to 500 μ g/g, with 2.0h
-1(v) air speed is by ABS1# sweetening agent bed, and sulphur content is less than 0.2 μ g/g in the oil.The inorganic sulfur of desulfuration adsorbent of the present invention in can effective elimination stock oil is described.The sulfur capacity of running terminal point desulfuration adsorbent is 30.1%.
Embodiment 13
Test oil is the straight-run spirit after refining (same with embodiment 5～7 raw materials used oil phases).Add n-butyl mercaptan and thiophene (by weight percentage, n-butyl mercaptan 70%, thiophene 30%) in stock oil, making its organic sulfur content is 30 μ g/g, with 2.0h
-1(v) air speed is by ABS2# sweetening agent bed, and sulphur content is less than 0.2 μ g/g in the oil.Present embodiment illustrates that desulfuration adsorbent of the present invention can effective elimination heterocycle sulfide.
Embodiment 14
The tubular reactor 3# desulfuration adsorbent 100ml that packs into.
Test oil is the straight-run spirit after refining (same with embodiment 5～7 raw materials used oil phases).In stock oil, add n-butyl mercaptan and hydrogen sulfide, make its total sulfur content increase to 200 μ g/g, with 2.0h
-1(v) air speed is by ABS3# sweetening agent bed, and sulphur content is less than 0.2 μ g/g in the sweet oil.The sulfur capacity of running terminal point desulfuration adsorbent is 26.3%.
Embodiment 15
Desulfuration adsorbent is 4#.Other conditions are with example 14.Turned round 1000 hours in, sulphur content is all less than 0.2 μ g/g in the sweet oil.The sulfur capacity of running terminal point desulfuration adsorbent is 31.2%.
Claims (9)
1, a kind of desulfuration adsorbent that is used to remove hydro carbons institute sulfur compound, comprise titanium dioxide, aluminium sesquioxide, silicon-dioxide and nickel, molybdenum bimetal component, weight with sorbent material is benchmark, content of titanium dioxide is 10～50%, aluminium sesquioxide content is 5～40%, dioxide-containing silica is 0～20%, is 20～50% in the nickel content of NiO, with MoO
3The molybdenum content of meter is 10～40%; The specific surface area of described sorbent material is 20～200m
2/ g, pore volume are 0.3～0.5ml/g, can several apertures be 6～20nm.
2, according to the described desulfuration adsorbent of claim 1, it is characterized in that the weight with sorbent material is benchmark, content of titanium dioxide is 15～40%; Aluminium sesquioxide content is 10～30%; Dioxide-containing silica is 5～10%.
3, according to the described desulfuration adsorbent of claim 1, it is characterized in that the weight with sorbent material is benchmark, the consisting of of metal component: the nickel content in NiO is 30～40%; With MoO
3The molybdenum content of meter is 15～25%.
4, the preparation method of each described desulfuration adsorbent of claim 1～3, its step comprises: mix hydrated aluminum oxide, titanium oxide powder, silicon-dioxide or silicon-containing compound (1) with extrusion aid or compound extrusion aid, add nitric acid or acetic acid solution, water then, mediate, add molybdate compound, nickel compound containing in the kneading process, mediate to being plastic shape; (2) extruded moulding; (3) wet bar drying, the roasting after the moulding; (4) cartridge reactor of packing into feeds hydrogen reducing; (5) draw off, seal up for safekeeping standby.
5, according to the preparation method of the described desulfuration adsorbent of claim 4, it is characterized in that the titanium oxide powder described in the step (1) is the titanium oxide powder through acid treatment, hydrolysis, washing, drying, pulverizing, wherein washing be wash with water to pH value be 6.5～7.5, drying is 100～120 ℃ of following dryings 6～10 hours.
6, according to the preparation method of the described desulfuration adsorbent of claim 4, it is characterized in that the molybdate compound described in the step (1) is selected from molybdic oxide, ammonium molybdate, ammonium paramolybdate, Ammonium Heptamolybdate or poly ammonium molybdate, nickel compound containing is selected from nickelous nitrate, nickel oxide, basic nickel carbonate, nickelous chloride, nickelous acetate or nickelous oxalate.
7, according to the preparation method of the described desulfuration adsorbent of claim 4, it is characterized in that the extrusion aid described in the step (1) is sesbania powder or citric acid, compound extrusion aid is the mixture of sesbania powder and citric acid, and wherein the weight of sesbania powder accounts for 40～80%, and the weight of citric acid accounts for 20～60%; The add-on of extrusion aid or compound extrusion aid is 3～7% of an adsorbent weight.
8, according to the preparation method of the described desulfuration adsorbent of claim 4, it is characterized in that the drying temperature described in the step (3) is 105～130 ℃, the time is 4～8 hours; The temperature of roasting is 550～750 ℃, and the time is 6～10 hours.
9,, it is characterized in that the reductive condition described in the step (4) is: 300～400 ℃ of temperature, time 5～20h, gas agent volume ratio 100～1000 according to the preparation method of the described desulfuration adsorbent of claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02144948 CN1205310C (en) | 2002-12-19 | 2002-12-19 | Hydrocarbon desulfurizing adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02144948 CN1205310C (en) | 2002-12-19 | 2002-12-19 | Hydrocarbon desulfurizing adsorbent |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100634535B1 (en) * | 2005-01-24 | 2006-10-13 | 삼성에스디아이 주식회사 | Zeolite adsorbent for desulfurization and manufacturing method thereof |
| KR101264330B1 (en) | 2006-02-18 | 2013-05-14 | 삼성에스디아이 주식회사 | Desulfurization device for fuel gas of fuel cell and desulfurizing method using the same |
| US8535518B2 (en) * | 2011-01-19 | 2013-09-17 | Saudi Arabian Oil Company | Petroleum upgrading and desulfurizing process |
| CN102512942B (en) * | 2011-12-20 | 2015-07-01 | 北京三聚环保新材料股份有限公司 | Low-temperature fine desulfurizer and its preparation method |
| US10752847B2 (en) | 2017-03-08 | 2020-08-25 | Saudi Arabian Oil Company | Integrated hydrothermal process to upgrade heavy oil |
| US10703999B2 (en) | 2017-03-14 | 2020-07-07 | Saudi Arabian Oil Company | Integrated supercritical water and steam cracking process |
| US10526552B1 (en) | 2018-10-12 | 2020-01-07 | Saudi Arabian Oil Company | Upgrading of heavy oil for steam cracking process |
| CN114433114B (en) * | 2020-10-31 | 2023-09-01 | 中国石油化工股份有限公司 | Liquid phase hydrogenation catalyst |
| CN112619590B (en) * | 2020-11-29 | 2022-12-09 | 上海绿强新材料有限公司 | Renewable hydrogen sulfide adsorbent and preparation method thereof |
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