CN101314733A - 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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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 the hydrogenation 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 and other organic acid can be generically and collectively referred to as petroleum 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 can be, make that the kind and the content of metal ion constantly rose in the crude oil, wherein with Ca for crude resources heaviness, peracid value and chemistry or the microbe oil production broad application day by day of exploitation
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 with oil in acidic components.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 price costlinesses have 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 to contain acid number crude oil and low acid number crude oil hybrid process, reduces the acid number of raw material.This way is subjected to 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, the following process device has been removed the problem of naphthenic acid corrosion from, the employing plain carbon stool gets final product, and can save great amount of investment for refinery.
US 5897769 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.
US 6063266 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 the group vib metal and/or the group VIII metal that load 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.
Stock oil of the present invention 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 be 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:
Fe(RCOO)
2+H
2S+H
2→FeS+RCH
3+H
2O
Ca(RCOO)
2+H
2S+H
2→CaS+RCH
3+H
2O
In the prior art of acid-containing raw oil hydrogenation deacidification, normally adopt fixed-bed reactor, and be that stock 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 stock 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 enter reactor from the up-flow reactor bottom, the catalyzer that stirs in the bed upwards floats, this moment, catalyst particles intergranular voidage increased, make 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 be evenly distributed in the reactor, 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 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 reactors, and can have one or more beds in each reactor.When having a plurality of reactor, the number of described reactor can be for 2～4, and when having a plurality of beds, the number of described 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 and the required active surface of reaction of reactant molecule, good performance is arranged in the hydrodemetallation (HDM) reaction process, adopted the shape of ellipsoid or Raschig ring on the other hand, increased the voidage between the catalyzer, both be applicable to the upflowing hydrogenator, also make metal can be evenly distributed in whole beds, avoid 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 to handle the acid-containing raw oil of high metal content under the low pressure condition, 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
The following examples will give further instruction to 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, and its total acid value is 2.58mgKOH/g as can be seen from Table 1, 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.As can be seen from Table 3, the total acid value of the product liquid of gained is 0.43mgKOH/g, and 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.As can be seen from Table 3, the total acid value of the product liquid of gained is 0.22mgKOH/g, and 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 |
| ＞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 (8)
1, a kind of method of 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, described hydrotreating catalyst contains a kind of alumina supporter and the group vib metal and/or the group VIII metal that load 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.
2, in accordance with the method for 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, in accordance with the method for 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, in accordance with the method for claim 1, it is characterized in that 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
5, in accordance with the method for claim 4, 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
6, in accordance with the method for 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.
7, according to claim 1 or 6 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, 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.
What 8, in accordance with the method for claim 1, it is characterized in that described hydrotreating catalyst is shaped as ellipsoid or Raschig ring.
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Family Cites Families (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 |
| CN1312256C (en) * | 2003-10-31 | 2007-04-25 | 中国石油化工股份有限公司 | Distillate oil hydrodeacidifying method |
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