CN100510011C - Method for eliminating petroleum acid in hydrocarbon oil - Google Patents
Method for eliminating petroleum acid in hydrocarbon oil Download PDFInfo
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- CN100510011C CN100510011C CNB2005101352333A CN200510135233A CN100510011C CN 100510011 C CN100510011 C CN 100510011C CN B2005101352333 A CNB2005101352333 A CN B2005101352333A CN 200510135233 A CN200510135233 A CN 200510135233A CN 100510011 C CN100510011 C CN 100510011C
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Abstract
The invention relates to a method for removing petroleum acid by mixing acid-containing hydrocarbon oil with catalyst at 200- 500 Deg. C in distillation tower. The invention is characterized in that: said catalyst is acid catalyst, which catalyzes the carboxyl of petroleum acid in the acid-containing hydrocarbon oil to disintegrate the petroleum acid into hydrocarbon ,carbon dioxide, carbon monoxide and water, and the gas product in distillation tower can be removed through evaporation timely, which is good for acid removal rate; the normal distillation tower can be improved by installing catalyst bed on bottom of tower; the acid-removed hydrocarbon oil can be separated from distillation tower with normal method, so the device investment is low and operation is simple.
Description
Technical field
The invention relates to a kind of acid stripping method, more specifically about a kind of method that removes petroleum acid.
Background technology
The acid of crude oil PetroChina Company Limited. is that acidic substance comprise mineral acid, phenols, mercaptan, aliphatic carboxylic acid and naphthenic acid, and wherein naphthenic acid is acidic substance main in the crude oil, and its content accounts for about 90 weight % of acidic substance.
In Crude Oil Processing, the oil acidic substance can be directly and the iron reaction, also can react with the protective membrane Iron sulfuret on the oil equipment, causes equipment corrosion.General petroleum products, as the acid number requirement is also arranged in gasoline, diesel oil, the kerosene quality index usually, too high acid number brings same etching problem to the user easily.If can not in refining process, remove petroleum acid, will influence end product quality, cause problems such as the potential safety hazard of equipment failure, equipment and environmental pollution.
Petroleum acid content in the crude oil generally adopts the size of total acid value (TAN) to represent its height.Restrain the required potassium hydroxide milligram number of formation testing [milligram (KOH)/gram] with 1 during total acid value is meant, can measure, as adopting the method mensuration of stipulating among the ASTM D664 by potentiometric titration.
At present, the method for the petroleum acid content in the reduction crude oil mainly contains: 1. add the alkali neutralisation; 2. physisorphtion; 3. solvent extraction process; 4. shortening method; 5. pyrolysis method (comprising the catalytic cracking solution).
US 5910242 discloses the method that a kind of shortening method reduces total acid value in the crude oil, this method is included in hydrogen and handles under the gas existence condition, under the pressure of 200-370 ℃ temperature and 239-13900 kPa, crude oil is contacted with Hydrobon catalyst, wherein, hydrogen is handled in the gas and is contained 0.05-25 mole % hydrogen sulfide.The deacidification effect of shortening method is relatively good, but the shortening method needs special high pressure resistant high temperature service, the facility investment height, and it also needs hydrogen in addition, so cost is higher.
USP 5928502 discloses the method that a kind of catalytic cracking solution reduces carboxylic acid content in the oil, but this method comprises the dispersed catalyzer in solvable or the dispersed oil is joined in the crude oil; Under the condition that does not have hydrogen to exist basically, under the pressure of 204.44-426.67 ℃ temperature and 6996.33 kPas, in reactor, the crude oil that is added with described catalyzer is heated; And use rare gas element to clean described reactor, the dividing potential drop sum of water vapour and carbon monoxide is maintained be lower than 344.75 kPas.Wherein, the catalyzer that this method is used contains metallic compound, described metal is selected from the group of being made up of the 5th subgroup metal, the 6th subgroup metal, the 7th subgroup metal and eight family's metals, and the example of described metallic compound comprises phospho-molybdic acid metal-salt, molybdenum naphthenate and molybdenum dialkyl-dithiophosphate.The shortcoming of this method is long reaction time, and coking problem is serious, and acid removal rate (being the carboxylic acid content reduced rate) is not high, and acid removal rate is the highest only to reach 51%.
Summary of the invention
The present invention seeks to overcome the low shortcoming of acid removal rate that existing employing catalytic cracking solution reduces the method for the petroleum acid content in the crude oil, provide a kind of acid removal rate the high method that removes petroleum acid.
The invention provides a kind of method that removes petroleum acid, this method is included under 200-500 ℃ the temperature, and acid-containing hydrocarbon oil is contacted with catalyzer, and wherein, described catalyzer is an an acidic catalyst, and acid-containing hydrocarbon oil contacts in distillation tower with catalyzer.
Catalyzer used in the present invention is an an acidic catalyst, this catalyzer plays katalysis to the carboxyl of acid-containing hydrocarbon oil PetroChina Company Limited. acid, make petroleum acid be decomposed into hydro carbons, carbonic acid gas, carbon monoxide and water, and acid-containing hydrocarbon oil contacts in distillation tower with catalyzer, the gaseous product that generates can steam from reaction system in time, helps improving acid removal rate; Only need conventional distillation tower is transformed, increase the deacidification that beds can be realized acid-containing hydrocarbon oil in distillation tower bottom, and the acid-containing hydrocarbon oil after the depickling can carry out conventional fractionation by distillation in distillation tower, obtain the acid-containing hydrocarbon oil of depickling, therefore facility investment is few, simple to operate.
Description of drawings
Fig. 1 is the synoptic diagram of an embodiment of the expression method that removes petroleum acid provided by the invention;
Fig. 2 is the synoptic diagram of another embodiment of the expression method that removes petroleum acid provided by the invention.
Embodiment
The method that removes petroleum acid provided by the invention is included under 200-500 ℃ the temperature, and acid-containing hydrocarbon oil is contacted with catalyzer, and wherein, described catalyzer is an an acidic catalyst, and acid-containing hydrocarbon oil contacts in distillation tower with catalyzer.
Described an acidic catalyst is preferably solid acid catalyst.Described solid acid catalyst can be Lewis acid (Lewis acid) catalyzer, protonic acid (Bronsted acid) catalyzer or their mixture.
Described Lewis acid (Lewis acid) can be selected from aluminum chloride, AlF
3, SnO
2-HL, ZnCl
2, in the solid phosphoric acid one or more.Described protonic acid (Bronsted acid) is selected from acidic molecular sieve.
Under the preferable case, described solid acid catalyst contains acidic molecular sieve and matrix.Gross weight with an acidic catalyst is a benchmark, and the content of acidic molecular sieve is 10-85 weight %, is preferably 20-80 weight %; The content of matrix is 15-90 weight %, is preferably 20-80 weight %.
Described molecular sieve can be selected from faujusite, mordenite, have in the zeolite of MFI structure, beta-zeolite, omega zeolite, phosphate aluminium molecular sieve, the layered molecular sieve one or more.
Described faujusite can be one or more in X type zeolite, y-type zeolite, the overstable gamma zeolite.Be preferably y-type zeolite and/or overstable gamma zeolite.
The zeolite of the described MFI of having structure can be one or more in ZSM-5 zeolite, ZRP zeolite, ZSM-8, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, the ZSM-48 zeolite.
Described phosphate aluminium molecular sieve can be one or more of SAPO molecular sieve kind, as among SAPO-11, SAPO-22, APO-5, SAPO-17, SAPO-34, SAPO-56, the SAPO-44 one or more.
Preferred molecular sieve is one or more in y-type zeolite, overstable gamma zeolite, mordenite, ZSM-5 zeolite, ZRP zeolite, the beta-zeolite.
Described molecular sieve can be hydrogen type molecular sieve or contain rare earth and/or the molecular sieve of phosphorus.The example of hydrogen type molecular sieve comprises one or more in Hydrogen y-type zeolite, overstable gamma zeolite, h-mordenite, Hydrogen ZSM-5 zeolite, ZRP-1 zeolite, the Hydrogen beta-zeolite.The example that contains the molecular sieve of rare earth and/or phosphorus comprises and contains rare earth and/or phosphorus y-type zeolite, contains rare earth and/or phosphorus overstable gamma zeolite, contains rare earth and/or phosphorus mordenite, contains rare earth and/or phosphorus ZSM-5 zeolite, ZRP-5 zeolite, contains in rare earth and/or the phosphorus beta-zeolite one or more.In oxide compound, the content of rare earth in molecular sieve is 0.5--25 weight %, is preferably 1--20 weight %.In oxide compound, the content of phosphorus in molecular sieve is 0.03-8 weight %, is preferably 0.05-5 weight %.
Described matrix can be various matrix commonly used, for example one or more in silicon oxide, aluminum oxide, amorphous aluminum silicide, alkaline earth metal oxide, zirconium white, titanium oxide and the boron oxide.Preferred matrix is one or more in silicon oxide, aluminum oxide and the amorphous aluminum silicide.
The shape of described solid acid catalyst can be an arbitrary shape, and for example, for fixed bed reaction, described solid acid catalyst can be bar shaped or various special-shaped shape, as cloverleaf pattern, Herba Galii Bungei shape, five leaves grass shape, Raschig ring shape.
Acid-containing hydrocarbon oil adopts the successive mode with contacting of catalyzer, and for example, continuously by the bed of catalyzer, acid-containing hydrocarbon oil carries out with contacting in distillation tower of catalyzer with acid-containing hydrocarbon oil.As depicted in figs. 1 and 2, catalyzer is put into formation beds 3 in the distillation tower 2, beds 3 is preferably placed at the bottom or the top, bottom of distillation tower 2.Acid-containing hydrocarbon oil is passed through to contact with beds 3 distillation tower 2 from the bottom of beds 3.
The condition that acid-containing hydrocarbon oil contacts with catalyzer comprises that temperature of reaction is 200-500 ℃, is preferably 250-480 ℃, and the total pressure of contact is the 0.05-0.4 MPa, is preferably the 0.09-0.35 MPa, wherein, and CO
2, CO and water vapour the dividing potential drop sum be not more than 0.002 MPa, be preferably the 0.0001-0.0015 MPa.
When contacting under acid-containing hydrocarbon oil and catalyzer 200-500 ℃ temperature, the petroleum acid in the acid-containing hydrocarbon oil is become hydrocarbon, CO by catalytic decomposition
2, CO and water, water is gasificated into water vapour under 200-500 ℃ temperature.For the reaction system that has gas to generate, in the process of reaction, the gas that generates is removed from reaction system, be favourable to the transformation efficiency that improves reaction.Therefore, in the method that removes petroleum acid provided by the invention, under the preferable case, in the catalytic while, shifting out the gaseous product that reaction generates to small part, is the 0.09-0.35 MPa with the total pressure that guarantees contact, is preferably the 0.1-0.3 MPa, wherein, and CO
2, CO and water vapour the dividing potential drop sum be not more than 0.002 MPa, be preferably the 0.0001-0.0015 MPa.
The condition that described acid-containing hydrocarbon oil contacts with catalyzer comprises that also liquid hourly space velocity is 0.1-100 hour-1, is preferably 0.2-80 hour-1.
According to specific embodiment of the present invention, as depicted in figs. 1 and 2, catalyzer is put into formation beds 3 in the distillation tower 2, beds 3 is preferably placed at the bottom or the top, bottom of distillation tower 2.Acid-containing hydrocarbon oil is heated to 200-500 ℃ with process furnace 1, is preferably 250-480 ℃, the acid-containing hydrocarbon oil after will heating then passes through to contact with beds 3 distillation tower 2 from the bottom of beds 3.
Acid-containing hydrocarbon oil and catalyzer in conventional distillation tower, contact can realize below several advantages:
1, the petroleum acid in the acid-containing hydrocarbon oil can steam from reaction system through gaseous product carbonic acid gas, carbon monoxide and the water vapour that catalytic decomposition generates in time, reduces the dividing potential drop of carbonic acid gas, carbon monoxide and water vapour, helps improving acid removal rate;
2, conventional distillation tower is transformed, increase the deacidification that beds can be realized acid-containing hydrocarbon oil in distillation tower bottom, and the acid-containing hydrocarbon oil after the depickling can carry out conventional fractionation by distillation in distillation tower, obtain the acid-containing hydrocarbon oil of depickling, therefore facility investment is few, simple to operate.
Method provided by the invention can remove the petroleum acid in any acid-containing hydrocarbon oil, described hydrocarbon ils is selected from mineral oil and cut thereof, as in crude oil, long residuum, vacuum residuum, vacuum gas oil, coker gas oil, aviation kerosene, hydrogenation tail oil, deasphalted oil, shale oil, lubricating oil, diesel oil, gasoline and the liquefied coal coil one or more.Be preferably in crude oil, gasoline, diesel oil, kerosene and the lubricating oil one or more.There is no particular limitation to the total acid value of described hydrocarbon ils in the present invention, for example can be 1-30 milligram (KOH)/gram.
Below by embodiment the present invention is described in more detail.
The specification of used material among the preparation embodiment:
Pseudo-boehmite: Shandong Aluminum Plant's Industrial products, Al in the butt
2O
3Content is 95 weight %, and solid content is 65 weight %.
The Chang Ling dry glue powder, Chang Ling refinery catalyst plant product, contents on dry basis is 73 weight %
The ZRP zeolite: Shandong, Shandong catalyst plant Industrial products, silica alumina ratio are 6.
Hyperastable Y-type RE (REUSY) type zeolite: Shandong, Shandong catalyst plant Industrial products, with RE
2O
3The content of rare earth of meter is 3.0 weight %.
REY type zeolite: Shandong, Shandong catalyst plant Industrial products, silica alumina ratio SiO
2/ Al
2O
3Be 5.0, with RE
2O
3The content of rare earth of meter is 18 weight %.
REHY type zeolite: Shandong, Shandong catalyst plant Industrial products, with RE
2O
3The content of rare earth of meter is 6 weight %.
SAPO type zeolite: Chang Ling refinery catalyst prod, silica alumina ratio are 10.
Solid phosphoric acid: trade(brand)name T-99, Shanghai Petroleum Chemical Engineering Institute product.
Preparation embodiment 1
With 3 kilograms go the sun dried up with 1 kilogram of Chang Ling dry glue powder, add 1 kilogram of pseudo-boehmite again, transfer pH=2-4 with hydrochloric acid, stir, wore out 1 hour down at 75 ℃, cool the temperature to below 60 ℃, add 1.7 kilograms of REHY, stir, filter to carry 80 ℃ of following baking ovens 4 hours, and be extruded into circumscribed circle diameter and be 1.4 millimeters trifolium-shaped bar, at room temperature with the ammonium acetate washing of PH=8.8,120 ℃ of oven dry, roasting obtained catalyst A in 7 hours under 630 ℃ of air atmospheres.
According to prepare embodiment 1 in identical method obtain catalyst B, different is that molecular sieve is 2 kilograms of USY.
With 0.5 kilogram of Chang Ling dry glue powder, add 1 kilogram of pseudo-boehmite with 3 kilograms of decationizing water again, transfer pH=2-4 with hydrochloric acid, stir, wore out 1 hour down at 75 ℃, cool the temperature to below 60 ℃, add 2.5 kilograms of REY, stir, filter and carried 80 ℃ of following baking ovens 4 hours, be extruded into 1.4 millimeters trilobal cross bar, at room temperature the ammonium acetate with PH=8.8 washs, 120 ℃ of oven dry, roasting obtained catalyzer C in 7 hours under 630 ℃ of air atmospheres.
Preparation embodiment 4
With 0.25 kilogram of Chang Ling dry glue powder, 0.75 the ZRP molecular sieve of kilogram pseudo-boehmite and 3 kilograms is polished on ball mill less than 100 purpose powders, under the room temperature the two is mixed, and adds an amount of nitric acid, water and sesbania powder, stir the pasty substance that mixture Cheng Yi is extruded.Be extruded into 1.2 millimeters trifolium-shaped bar on banded extruder, at room temperature the ammonium acetate with PH=8.8 washs, 120 ℃ of oven dry, and roasting obtained catalyzer D in 8 hours under 550 ℃ of air atmospheres.
Preparation embodiment 5
According to identical that method makes catalyzer E with preparation embodiment 4, different is that molecular sieve is 4 kilograms of SAPO34.
Preparation embodiment 6
Remove the dried up 1 kilogram of pseudo-boehmite of sun with 3 kilograms, transfer pH=2-4, stir with hydrochloric acid, 75 ℃ aging 1 hour down, cool the temperature to below 60 ℃, add 0.5 kilogram of ZnCl
2, stir, filter to carry 80 ℃ of following baking ovens 4 hours, be extruded into circumscribed circle diameter and be 1.4 millimeters trifolium-shaped bar, at room temperature with the ammonium acetate washing of PH=8.8,120 ℃ of oven dry, roasting obtained catalyzer F in 7 hours under 630 ℃ of air atmospheres.
Used raw material among the embodiment:
Raw material G: with total acid value is that the four wire loop alkanoic acids that subtract of 100 milligrams (KOH)/gram join in the petrol and diesel oil mixture, makes the total acid value of mixture reach 24.54 milligrams (KOH)/gram, should mix oil sample and be used as raw material G;
Raw material H: total acid value is the high-acid crude oil of 12.52 milligrams (KOH)/gram.
Raw material G, raw material H essential property are as shown in Table 1 and Table 2.
Embodiment 1
This embodiment is used to illustrate the method that removes petroleum acid provided by the invention.
As shown in Figure 1, raw material G is heated to 280 ℃ in process furnace 1, then with 75 hours
-1Liquid hourly space velocity enter in the distillation tower 2 (wherein, the diameter of distillation tower is 32 millimeters, highly is 6 meters).In temperature is that 280 ℃, pressure are 0.14 MPa and CO
2, CO and water vapour the dividing potential drop sum be under the condition of 0.0004 MPa, raw material G contacts with the catalyst A bed (height of beds is 0.8 meter) that is placed in 1/3 place, top, distillation tower 2 bottoms.
Light ends after the depickling is fractionated into gasoline and diesel oil in distillation tower 2.Adopt the total acid value of the methods analyst reaction liquid product of stipulating among the ASTMD664, acid removal rate is 90%.
Wherein, total acid value * 100% of acid removal rate=(total acid value of raw material-reaction liquid product total acid value)/raw material
This embodiment is used to illustrate the method that removes petroleum acid provided by the invention.
As shown in Figure 1, raw material G is heated to 320 ℃ in process furnace 1, then with 60 hours
-1Liquid hourly space velocity enter in the distillation tower 2 (wherein, the diameter of distillation tower is 32 millimeters, highly is 6 meters).In temperature is that 320 ℃, pressure are 0.15 MPa and CO
2, CO and water vapour the dividing potential drop sum be under the condition of 0.0005 MPa, raw material G contacts with the catalyst B bed (height of beds is 0.6 meter) that is placed in 1/3 place, top, distillation tower 2 bottoms.
Light ends after the depickling is fractionated into gasoline and diesel oil in distillation tower 2.Adopt the total acid value of the methods analyst reaction liquid product of stipulating among the ASTMD664, and be 91% according to the acid removal rate that the method identical with embodiment 1 calculated raw material G.
This embodiment is used to illustrate the method that removes petroleum acid provided by the invention.
As shown in Figure 2, raw material G is heated to 400 ℃ in process furnace 1, then with 8 hours
-1Liquid hourly space velocity enter in the distillation tower 2 (wherein, the diameter of distillation tower bottom is 100 millimeters, and upper diameter is 32 millimeters, highly is 6 meters).In temperature is that 400 ℃, pressure are 0.17 MPa and CO
2, CO and water vapour the dividing potential drop sum be under the condition of 0.0006 MPa, raw material G contacts with the catalyzer C bed that is placed in distillation tower 2 bottoms (height of beds is 1 meter).
Light ends after the depickling is fractionated into gasoline and diesel oil in distillation tower 2.Adopt the total acid value of the methods analyst reaction liquid product of stipulating among the ASTMD664, and be 95% according to the acid removal rate that the method identical with embodiment 1 calculated raw material G.
Embodiment 4
This embodiment is used to illustrate the method that removes petroleum acid provided by the invention.
As shown in Figure 2, raw material H is heated to 450 ℃ in process furnace 1, then with 25 hours
-1Liquid hourly space velocity enter in the distillation tower 2 (wherein, the diameter of distillation tower bottom is 100 millimeters, and upper diameter is 32 millimeters, highly is 6 meters).In temperature is that 450 ℃, pressure are 0.19 MPa and CO
2, CO and water vapour the dividing potential drop sum be under the condition of 0.0006 MPa, raw material H contacts with the catalyzer D bed that is placed in distillation tower 2 bottoms (height of beds is 1.2 meters).
Light ends after the depickling is fractionated into gasoline, kerosene, diesel oil and heavy oil in distillation tower 2.Adopt the total acid value of the methods analyst reaction liquid product of stipulating among the ASTM D664, and be 90% according to the acid removal rate that the method identical with embodiment 1 calculated raw material H.
Embodiment 5
This embodiment is used to illustrate the method that removes petroleum acid provided by the invention.
As shown in Figure 2, raw material H is heated to 450 ℃ in process furnace 1, then with 25 hours
-1Liquid hourly space velocity enter in the distillation tower 2 (wherein, the diameter of distillation tower bottom is 100 millimeters, and upper diameter is 32 millimeters, highly is 6 meters).In temperature is that 450 ℃, pressure are 0.25 MPa and CO
2, CO and water vapour the dividing potential drop sum be under the condition of 0.0006 MPa, raw material H contacts with the catalyzer E bed that is placed in distillation tower 2 bottoms (height of beds is 1.2 meters).
Light ends after the depickling is fractionated into gasoline, kerosene, diesel oil and heavy oil in distillation tower 2.Adopt the total acid value of the methods analyst reaction liquid product of stipulating among the ASTM D664, and be 92% according to the acid removal rate that the method identical with embodiment 1 calculated raw material H.
Embodiment 6
This embodiment is used to illustrate the method that removes petroleum acid provided by the invention.
As shown in Figure 2, raw material H is heated to 420 ℃ in process furnace 1, then with 10 hours
-1Liquid hourly space velocity enter in the distillation tower 2 (wherein, the diameter of distillation tower bottom is 100 millimeters, and upper diameter is 32 millimeters, highly is 6 meters).In temperature is that 420 ℃, pressure are 0.3 MPa and CO
2, CO and water vapour the dividing potential drop sum be under the condition of 0.0005 MPa, raw material H contacts with the solid phosphoric acid T-99 beds that is placed in distillation tower 2 bottoms (height of beds is 1.7 meters).
Light ends after the depickling is fractionated into gasoline, kerosene, diesel oil and heavy oil in distillation tower 2.Adopt the total acid value of the methods analyst reaction liquid product of stipulating among the ASTM D664, and be 92.5% according to the acid removal rate that the method identical with embodiment 1 calculated raw material H.
Embodiment 7
This embodiment is used to illustrate the method that removes petroleum acid provided by the invention.
As shown in Figure 2, raw material H is heated to 420 ℃ in process furnace 1, then with 10 hours
-1Liquid hourly space velocity enter in the distillation tower 2 (wherein, the diameter of distillation tower bottom is 100 millimeters, and upper diameter is 32 millimeters, highly is 6 meters).In temperature is that 420 ℃, pressure are 0.35 MPa and CO
2, CO and water vapour the dividing potential drop sum be under the condition of 0.0005 MPa, raw material H contacts with the catalyzer F bed that is placed in distillation tower 2 bottoms (height of beds is 1.7 meters).
Light ends after the depickling is fractionated into gasoline, kerosene, diesel oil and heavy oil in distillation tower 2.Adopt the total acid value of the methods analyst reaction liquid product of stipulating among the ASTM D664, and be 95% according to the acid removal rate that the method identical with embodiment 1 calculated raw material H.
Table 1: the essential property of raw material G
| Project | Character |
| Density (20 ℃), kilogram/rice 3 | 815.7 |
| Total acid value, milligram KOH/ gram | 24.54 |
| Aromaticity content, volume % | 25.3 |
| Olefin(e) centent, volume % | 21.0 |
| Total sulfur content, weight % | 0.113 |
| Boiling range ℃ initial boiling point 10% vaporization temperature 20% vaporization temperature 50% vaporization temperature 90% vaporization temperature 98% vaporization temperature final boiling point | 70 95 122 142 279 295 306 |
| Residual quantity, volume % | 0.8 |
| The viscosity millimeter 2/ second (20 ℃) | 1.506 |
| Existent gum, milligram/100 milliliters | 4.6 |
The essential property of table 2 raw material H
| Project | Character |
| Density (20 ℃), gram per centimeter 3Kinematic viscosity (80 ℃), millimeter 2/ second carbon residue, weight % acid number, milligram KOH/ gram sulphur, weight % nitrogen, weight % | 0.9224 20.38 5.67 12.52 0.32 0.42 |
| Colloid, weight % bituminous matter, weight % wax content, weight % | 16.7 0.1 4.2 |
| Metal content, microgram/gram iron nickel vanadium | 3.5 25.3 0.6 |
| Distillation yield, 15～200 ℃ 200～350 ℃ 350～500 ℃ of weight %〉500 ℃ | 7.21 22.1 29.73 40.96 |
| The crude oil classification | Low-sulfur cycloalkanes-intermediate base |
Claims (14)
1, a kind of method that removes the petroleum acid in the hydrocarbon ils, this method are included under 200-500 ℃ the temperature, and acid-containing hydrocarbon oil is contacted with catalyzer, it is characterized in that described catalyzer is an an acidic catalyst, and acid-containing hydrocarbon oil contacts in distillation tower with catalyzer.
2, method according to claim 1, wherein, described an acidic catalyst is a solid acid catalyst, described solid acid catalyst is lewis acid catalyst, bronsted acid catalyst or their mixture.
3, method according to claim 2, wherein, described Lewis acid is selected from AlCl
3, AlF
3, SnO
2-HL, ZnCl
2, in the solid phosphoric acid one or more.
4, method according to claim 2, wherein, described bronsted acid catalyst contains acidic molecular sieve and matrix, is benchmark with the gross weight of solid acid catalyst, and the content of molecular sieve is 10-85 weight %, and the content of matrix is 15-90 weight %.
5, method according to claim 4 wherein, is a benchmark with the gross weight of solid acid catalyst, and the content of molecular sieve is 20-80 weight %, and the content of matrix is 20-80 weight %.
6, method according to claim 4, wherein, described molecular screening one or more in faujusite, mordenite, zeolite, beta-zeolite, omega zeolite, phosphate aluminium molecular sieve, layered molecular sieve with MFI structure.
7, method according to claim 6, wherein, described faujusite is one or more in X type zeolite, the y-type zeolite; The zeolite of the described MFI of having structure is one or more in ZSM-5 zeolite, ZRP zeolite, ZSM-8, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, the ZSM-48 zeolite; Described phosphate aluminium molecular sieve is one or more in the SAPO molecular sieve.
8, method according to claim 7, wherein, described y-type zeolite is an overstable gamma zeolite.
9, method according to claim 4, wherein, described matrix is one or more in silicon oxide, aluminum oxide and the amorphous aluminum silicide.
10, method according to claim 1, wherein, described catalyzer is the fixed bed catalyzer, beds is placed in the bottom or the top, bottom of distillation tower.
11, method according to claim 1, wherein, the condition that acid-containing hydrocarbon oil contacts with catalyzer comprises that the total pressure that contacting temperature is 200-500 ℃, contact is 0.05-0.4 MPa, CO
2, CO and water vapour the dividing potential drop sum be not more than 0.002 MPa, liquid hourly space velocity is 0.1-100 hour
-1
12, method according to claim 11, wherein, the condition that acid-containing hydrocarbon oil contacts with catalyzer comprises that the total pressure that contacting temperature is 250-480 ℃, contact is 0.09-0.35 MPa, CO
2, CO and water vapour the dividing potential drop sum be that 0.0001-0.0015 MPa, liquid hourly space velocity are 0.2-80 hour
-1
13, method according to claim 1, wherein, acid-containing hydrocarbon oil with before catalyzer contacts, is heated to 200-500 ℃ with acid-containing hydrocarbon oil in being incorporated into distillation tower.
14, method according to claim 1, wherein, described hydrocarbon ils is selected from one or more in crude oil, long residuum, vacuum residuum, vacuum gas oil, coker gas oil, aviation kerosene, hydrogenation tail oil, deasphalted oil, shale oil, lubricating oil, diesel oil, gasoline and the liquefied coal coil.
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|---|---|---|---|
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|---|---|---|---|
| CNB2005101352333A CN100510011C (en) | 2005-12-27 | 2005-12-27 | Method for eliminating petroleum acid in hydrocarbon oil |
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Non-Patent Citations (3)
| Title |
|---|
| 吴明清.化工时刊，第11卷第5期. 1997 |
| 石油馏分中环烷酸分离. 陆婉珍 |
| 石油馏分中环烷酸分离. 陆婉珍；吴明清.化工时刊，第11卷第5期. 1997 * |
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