CN101314733B - Hydrogenation depickling method for high-metal acid containing primary oil - Google Patents
Hydrogenation depickling method for high-metal acid containing primary oil Download PDFInfo
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- CN101314733B CN101314733B CN2007100998427A CN200710099842A CN101314733B CN 101314733 B CN101314733 B CN 101314733B CN 2007100998427 A CN2007100998427 A CN 2007100998427A CN 200710099842 A CN200710099842 A CN 200710099842A CN 101314733 B CN101314733 B CN 101314733B
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Abstract
A method for hydrogenating and deacidifying high-metal acid crude oil comprises the following steps: contacting acid crude oil and hydrogen with a hydrogenation catalyst in an up-flow reactor to carry out hydrogenation reaction, cooling and separating the reaction resultants to obtain hydrogen-rich gas and a liquid product, and circulating the hydrogen-rich gas to the up-flow reactor, wherein thehydrogenation catalyst contains an aluminum oxide carrier and VIB-group and/or VIII-group metals loaded on the carrier. The method can process acid crude oil with high metal content under low pressure condition, and can effectively remove acid substances in the acid crude oil while preventing activity degeneration of the catalyst and blockage of catalyst bed due to the deposition of metals, particularly iron, calcium, etc., thus achieving long-period operation of the device.
Description
Technical field
The invention belongs to a kind ofly in the method that has under the situation of hydrogen refining hydrocarbon ils, more particularly, is a kind of method of high-metal acid containing primary oil hydrogenation deacidification.
Background technology
Acidic components in the crude oil generally are meant naphthenic acid, other carboxylic acid, and mineral acid, phenols, mercaptan etc., wherein naphthenic acid can be generically and collectively referred to as petroleum acid with other organic acid.Naphthenic acid accounts for more than 85% in petroleum acid content, therefore traditionally petroleum acid generally is called naphthenic acid.What of acidic components in the crude oil are the size of acid value for crude oil reflected.When acid value for crude oil can cause equipment corrosion greater than 0.5mgKOH/g, so usually acid number is referred to as acid-containing raw oil greater than the crude oil of 0.5mgKOH/g.At present the output of acid-containing raw oil accounts for about 5% of global crude oil ultimate production every year on the crude oil market, the world, and annual also with 0.3% speed increment.
In recent years, along with the crude resources that can supply exploit heaviness, peracid value and chemistry or microbe oil production broad application day by day, made that the kind and the content of metals ion constantly rose in the crude oil, wherein with Ca
2+The content ascensional range is particularly outstanding.For example, the total acid value of domestic Liaohe River viscous crude is 2.10mgKOH/g, Ca
2+Content is up to 284 μ g/g, external the Sudan commingled crude acid number 13.82mgKOH/g, Ca
2+Content reaches as high as 1600 μ g/g.Therefore, how effectively high-metal acid containing primary oil being handled, is present problem demanding prompt solution.
Because acid-containing raw oil has corrodibility, refinery is for reducing the influence of petroleum acid corrosive, with in the various basic cpds and the acidic components in the oil.But the soap that oil carboxylic acid and alkali reaction form can make the heavy-gravity emulsification of crude oil, causes difficulty for the desalting and dewatering of crude oil, makes to take off salts contg rising in the crude oil of back, influences the following process of crude oil.Another kind of way is exactly the erosion-resisting metallic substance of a large amount of uses in refining equipment.Because these material prices are expensive, increased the oil refining cost, particularly concerning existing oil refining apparatus, adopt new anticorrosive, unrealistic.The third way adds inhibiter exactly in crude oil.But inhibiter can influence the following process process, reduces activity of such catalysts and life-span.The 4th kind of way also is the most frequently used method, is with containing acid number crude oil and low acid number crude oil hybrid process, reducing the acid number of raw material.This way receives the restriction of low acid number oil supply amount of refinery and petroleum tank reserves usually.The 5th kind of method is hydrogenation depickling method; This method can fundamentally solve the influence that acid-containing raw oil brings to processing; After the acid-containing raw oil hydrotreatment, naphthenic acid can be removed fully, and the following process device has been removed the problem of naphthenic acid corrosion from; The employing plain carbon stool gets final product, and can practice thrift great amount of investment for refinery.
US5897769 discloses a kind of method of acid-containing raw oil selective hydrogenation depickling, and adopting a kind of aperture is the catalyzer of 5.0～8.5nm, 200～370 ℃ of temperature, reacts under the condition of pressure 0～13.7MPa.This method can the selectively removing acid-containing raw oil in the lower molecular weight naphthenic acid.
US6063266 discloses a kind of method of hydrogenation crude depickling, and this method adopts NiMo or CoMo type catalyzer, 100～300 ℃ of temperature, and optionally depickling under the condition of pressure 0.1～5MPa, and do not remove sulfide and nitride.
Above prior art acidic substance in can effective elimination crude oil, but what handle all is that metal content is low, the especially low crude oil of iron and calcium contents.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of hydrogenation depickling method of high-metal acid containing primary oil.
Method provided by the invention comprises: acid-containing raw oil and hydrogen contact with hydrotreating catalyst in up-flow reactor and carry out the hydrotreatment reaction; Its resultant of reaction obtains hydrogen-rich gas and product liquid after refrigerated separation; The hydrogen-rich gas of gained loops back up-flow reactor; Described hydrotreating catalyst contains a kind of alumina supporter and loads on group vib metal and/or the group VIII metal on this carrier; Wherein the group vib metal is selected from molybdenum and/or tungsten, and the group VIII metal is selected from cobalt and/or nickel.
The raw oil that the present invention adopted is high-metal acid containing primary oil, the high acid-containing raw oil of iron and calcium contents particularly, and the acid number of its crude oil is at least 0.5mgKOH/g, and equipment is had bigger corrodibility.And contain metallic impurity such as more calcium, iron, nickel, vanadium in this crude oil, the content of its iron and calcium is at least 15 μ g/g, and perhaps the content of iron and calcium is at least 20 μ g/g.Wherein most of calcium and iron exist with forms such as organic acid salt, phenates, and nickel and vanadium then exist with the porphyrin compound form.These metallic impurity are difficult to removed in the preprocessing process of Desalting and Dewatering from Crude Oil, thereby can have influence on follow-up hydrogenation deacidification process.These metallic impurity can react with the hydrogen sulfide in the recycle hydrogen in hydrogenation process, generate metallic sulfide and are deposited on the hydrogenation catalyst bed:
In the prior art of acid-containing raw oil hydrogenation deacidification, normally adopt fixed-bed reactor, and be that raw oil and hydrogen from up to down pass through beds.When adopting this prior art to process high-metal acid containing primary oil; The settling of these metallic sulfides not only can seal the activity of hydrocatalyst center; Activity of hydrocatalyst is reduced, and when these sulfide when hydrogenation catalyst deposits in a large number, also can seriously hinder raw oil and recycle hydrogen proper flow at beds; Make that hydrogenator inner catalyst bed pressure drop lift velocity is too fast, thereby cause shorten greatly the running period of device.Therefore, the present invention adopts the upflowing hydrogenator and selects special hydrotreating catalyst for use, thus the defective of being brought when having overcome the high metal content acid-containing raw oil of above-mentioned processing.
The logistics direction of described up-flow reactor is mobile from bottom to top, slightly microdilatancy of catalyzer in the bed, and described beds cubical expansivity is no more than 5%.High-metal acid containing primary oil and hydrogen can mix the back from the up-flow reactor bottom feed, also can be respectively from up-flow reactor lower side and bottom feed.Preferred feeding manner is together from the up-flow reactor bottom feed after high-metal acid containing primary oil and hydrogen mix.
High-metal acid containing primary oil and hydrogen get into reactor drum from the up-flow reactor bottom; Catalyzer in the stirring bed is to float; This moment, catalyst particles intergranular voidage increased, and made that the impurity such as metal, solid particulate matter and bituminous matter in the high-metal acid containing primary oil can not be deposited on the reactor inlet place, but was evenly distributed in the reactor drum; Thereby avoided when using fixed-bed reactor, these impurity very easily are deposited on reactor head and cause the too fast defective of reactor pressure decrease rising.
Simultaneously, because the beds cubical expansivity of the up-flow reactor that the present invention adopts is controlled at below 5%, under this bed expansion rate, bed expansion is even and fluctuation is very little, and the distribution of granules of catalyst in bed also relatively evenly.Expansion to a certain degree makes beds become loose, and bigger holding solid PM for particulate matter, the space of metal impurities are provided, and makes them can be evenly distributed in whole beds, avoids all being deposited on the ingress and the pressure drop fast rise that causes.
In method of the present invention, the up-flow reactor that is adopted can comprise one or more reactor drums, and in each reactor drum, can have one or more beds.When having a plurality of reactor drum, the number of said reactor drum can be for 2～4, and when having a plurality of beds, the number of said bed can be 2～4.
The reaction conditions of described hydrotreatment is: hydrogen dividing potential drop 1.0～6.5MPa, 100～380 ℃ of temperature of reaction, hydrogen to oil volume ratio 50～600Nm
3/ m
3, volume space velocity 0.1～10.0h
-1The reaction conditions of preferred described hydrotreatment is: hydrogen dividing potential drop 1.5～6.0MPa, 150～370 ℃ of temperature of reaction, hydrogen to oil volume ratio 100～500Nm
3/ m
3, volume space velocity 0.2～8.0h
-1
Described hydrotreating catalyst be benchmark with the gross weight of catalyzer, and in oxide compound, the content of molybdenum and/or tungsten is 0.5～15 weight %, and the content of cobalt and/or nickel is 0.3～8 weight %, and surplus is an alumina supporter.
Described alumina supporter is a kind of alumina supporter of bimodal hole, and its pore volume is 0.8～1.6 a milliliter/gram, and specific surface area is 150～350 meters
2/ gram, the aperture accounts for total pore volume 40～90% at the pore volume of 10～30 nanometers, and the aperture accounts for total pore volume 10～50% at the pore volume of 100～2000 nanometers.
Described hydrotreating catalyst be shaped as ellipsoid or Raschig ring.
The preferred hydrotreating catalyst of the present invention; Be catalyzer on the one hand with bimodal pore distribution; Take into account the diffusion process active surface required of reactant molecule, good performance is arranged in the HDM reaction process, adopted the shape of ellipsoid or Raschig ring on the other hand with reaction; Increased the voidage between the catalyzer; Both be applicable to the upflowing hydrogenator, and also made metal can be evenly distributed in whole beds, and avoided all being deposited on the ingress and the pressure drop fast rise that causes.Therefore adopt the preferred hydrotreating catalyst of the present invention can slow down the deactivation rate of catalyzer, prolong the running period of catalyzer.
Advantage of the present invention is under the low pressure condition, to handle the acid-containing raw oil of high metal content; Not only can effective elimination acid-containing raw oil middle acid substance; Also can avoid particularly problem such as the catalyst activity reduction that causes of metal deposition such as iron, calcium and beds obstruction of metal; Effectively slow down the lift velocity of beds pressure drop, thus the long-term operation of implement device.
Embodiment
Following embodiment will further explain the present invention, but therefore not limit the present invention.
The used raw material of embodiment is a kind of acid-containing raw oil, and its character is as shown in table 1, can find out that from table 1 its total acid value is 2.58mgKOH/g, and the content of iron and calcium reaches 43.1 μ g/g, is the acid-containing raw oil of high metal content.
The trade names RUF-1 of the hydrotreating catalyst that embodiment is used is the Chang Ling catalyst plant production of Sinopec catalyzer branch office, and the composition and the physico-chemical property of catalyzer are as shown in table 2.
Embodiment 1
Acid-containing raw oil contacts with hydrotreating catalyst RUF-1 in up-flow reactor with hydrogen, at hydrogen dividing potential drop 3.0MPa, and 300 ℃ of temperature of reaction, hydrogen to oil volume ratio 200Nm
3/ m
3, liquid hourly space velocity 4.0h
-1Condition under carry out hydrotreatment reaction, its resultant of reaction obtains hydrogen-rich gas and product liquid after refrigerated separation, the hydrogen-rich gas of gained loops back up-flow reactor, the main character of the product liquid of gained is as shown in table 3.Can find out that from table 3 total acid value of the product liquid of gained is 0.43mgKOH/g, acid removal rate is 83.3%, and the content of iron and calcium is respectively 1.9 μ g/g and 1.5 μ g/g in the product, and deferrization rate and decalcification rate are respectively up to 82.6% and 94.8%.
Embodiment 2
Acid-containing raw oil contacts with hydrotreating catalyst RUF-1 in up-flow reactor with hydrogen, at hydrogen dividing potential drop 5.0MPa, and 320 ℃ of temperature of reaction, hydrogen to oil volume ratio 200Nm
3/ m
3, liquid hourly space velocity 3.0h
-1Condition under carry out hydrotreatment reaction, its resultant of reaction obtains hydrogen-rich gas and product liquid after refrigerated separation, the hydrogen-rich gas of gained loops back up-flow reactor, the main character of the product liquid of gained is as shown in table 3.Can find out that from table 3 total acid value of the product liquid of gained is 0.22mgKOH/g, acid removal rate is 91.5%, and the content of iron and calcium is respectively 0.9 μ g/g and 0.5 μ g/g in the product, and deferrization rate and decalcification rate are respectively up to 93.7% and 98.3%.
Table 1
| Density (20 ℃), g/cm 3 | 0.9417 |
| Total acid value, mgKOH/g | 2.58 |
| Metal content, μ g/g | |
| Ni | 20.5 |
| V | 2.5 |
| Fe | 14.2 |
| Ca | 28.9 |
Table 2
| Character | |
| Crushing strength radially, the N/ grain | 25 |
| Wear rate, % | 0.1 |
| Total pore volume, ml/g | 0.80 |
| Specific surface, m 2/g | 150 |
| Can several bore dias, nm | 15.0 |
| The 100nm pore volume, ml/g | 0.25 |
| Metal content, weight % | |
| MoO 3 | 4.6 |
| NiO | 1.6 |
| Shape | Ellipsoid |
Table 3
| Product property | Embodiment 1 | Embodiment 2 |
| Density (20 ℃), g/cm 3 | 0.9486 | 0.9512 |
| Total acid value, mgKOH/g | 0.43 | 0.22 |
| Metal content, μ g/g | ||
| Ni | 19.8 | 18.6 |
| V | 2.1 | 1.8 |
| Fe | 1.9 | 0.9 |
| Ca | 1.5 | 0.5 |
| Acid removal rate, % | 83.3 | 91.5 |
| The deferrization rate, % | 82.6 | 93.7 |
| The decalcification rate, % | 94.8 | 98.3 |
Claims (7)
1. the method for a high-metal acid containing primary oil hydrogenation deacidification; It is characterized in that acid-containing raw oil and hydrogen contact with hydrotreating catalyst in up-flow reactor carries out the hydrotreatment reaction; Its resultant of reaction obtains hydrogen-rich gas and product liquid after refrigerated separation; The hydrogen-rich gas of gained loops back up-flow reactor, and described hydrotreating catalyst contains a kind of alumina supporter and loads on group vib metal and/or the group VIII metal on this carrier, and wherein the group vib metal is selected from molybdenum and/or tungsten; The group VIII metal is selected from cobalt and/or nickel; The reaction conditions of described hydrotreatment is: hydrogen dividing potential drop 1.0～6.5MPa, 100～380 ℃ of temperature of reaction, hydrogen to oil volume ratio 50～600Nm
3/ m
3, volume space velocity 0.1～10.0h
-1
2. according to the described method of claim 1, it is characterized in that described acid-containing raw oil is a high-metal acid containing primary oil, the content of its iron and calcium is at least 15 μ g/g.
3. according to the described method of claim 2, it is characterized in that described acid-containing raw oil is a high-metal acid containing primary oil, the content of its iron and calcium is at least 20 μ g/g.
4. according to the described method of claim 1, it is characterized in that the reaction conditions of described hydrotreatment is: hydrogen dividing potential drop 1.5～6.0MPa, 150～370 ℃ of temperature of reaction, hydrogen to oil volume ratio 100～500Nm
3/ m
3, volume space velocity 0.2～8.0h
-1
5. according to the described method of claim 1, it is characterized in that described hydrotreating catalyst, is benchmark with the gross weight of catalyzer; And in oxide compound; The content of molybdenum and/or tungsten is 0.5～15 weight %, and the content of cobalt and/or nickel is 0.3～8 weight %, and surplus is an alumina supporter.
6. according to claim 1 or 5 described methods, it is characterized in that described alumina supporter is a kind of alumina supporter of bimodal hole, its pore volume is 0.8～1.6 a milliliter/gram, and specific surface area is 150～350 meters
2/ gram, the aperture accounts for total pore volume 40～90% at the pore volume of 10～30 nanometers, and the aperture accounts for total pore volume 10～50% at the pore volume of 100～2000 nanometers.
7. according to the described method of claim 1, what it is characterized in that described hydrotreating catalyst is shaped as ellipsoid or Raschig ring.
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| CN101314733B true CN101314733B (en) | 2012-07-25 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443417B (en) * | 2010-10-13 | 2014-03-05 | 中国石油化工股份有限公司 | Hydrogenation treatment method for high-acid hydrocarbon oil |
| CN102453529A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Method for processing heavy material by using up-flow reactor system |
| CN102553558A (en) * | 2010-12-30 | 2012-07-11 | 中国石油天然气集团公司 | Catalyst used for reducing acid number of crude oil |
| CN102380397B (en) * | 2011-09-16 | 2013-07-31 | 中国海洋石油总公司 | Preparation method of distillate oil hydrogenation and deacidification catalyst |
| CN103059933B (en) * | 2011-10-24 | 2015-02-25 | 中国石油化工股份有限公司 | Hydrotreating method of high-acid high-calcium heavy crude oil |
| CN104263407A (en) * | 2014-07-26 | 2015-01-07 | 何巨堂 | Hydrocarbon hydrogenation method with up-flow bed layer and fixed bed operated in series |
| CN104232157A (en) * | 2014-07-28 | 2014-12-24 | 何巨堂 | Hydrocarbon hydrogenation method with particulate matter settling region and reactor adopting hydrocarbon hydrogenation method |
| CN104250566A (en) * | 2014-07-29 | 2014-12-31 | 何巨堂 | Hydrogenation method of inferior hydrocarbons containing easy-to-hydrogenolyze metallic compounds |
| CN104194829A (en) * | 2014-07-29 | 2014-12-10 | 何巨堂 | Inferior hydrocarbon hydrogenation method using self-produced ferric sulfide as pre-hydrorefining catalyst |
| CN109897664B (en) * | 2017-12-11 | 2021-04-06 | 中国石油化工股份有限公司 | Hydrotreating method for acid-containing crude oil |
| CN109897668B (en) * | 2017-12-11 | 2021-04-06 | 中国石油化工股份有限公司 | Processing method of acid-containing crude oil |
| CN109897669B (en) * | 2017-12-11 | 2021-04-06 | 中国石油化工股份有限公司 | Hydrotreating method for acid-containing crude oil |
| CN110180558B (en) * | 2018-05-17 | 2022-05-10 | 北京三聚环保新材料股份有限公司 | Biomass hydrogenation liquefaction catalyst, preparation method thereof and biomass hydrogenation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5897769A (en) * | 1997-08-29 | 1999-04-27 | Exxon Research And Engineering Co. | Process for selectively removing lower molecular weight naphthenic acids from acidic crudes |
| CN1611576A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Distillate oil hydrodeacidifying method |
-
2007
- 2007-05-31 CN CN2007100998427A patent/CN101314733B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5897769A (en) * | 1997-08-29 | 1999-04-27 | Exxon Research And Engineering Co. | Process for selectively removing lower molecular weight naphthenic acids from acidic crudes |
| CN1611576A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Distillate oil hydrodeacidifying method |
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