CN1024675C - Process for removing mercury or arsenic from hydrocarbons - Google Patents
Process for removing mercury or arsenic from hydrocarbons Download PDFInfo
- Publication number
- CN1024675C CN1024675C CN90101386A CN90101386A CN1024675C CN 1024675 C CN1024675 C CN 1024675C CN 90101386 A CN90101386 A CN 90101386A CN 90101386 A CN90101386 A CN 90101386A CN 1024675 C CN1024675 C CN 1024675C
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- Prior art keywords
- mercury
- metal
- catalyzer
- trapping agent
- arsenic
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-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
Abstract
For removing mercury and any arsenic in hydrocarbon charges containing mercury and sulfur, the charge is contacted with an arsenic collecting material having catalytic properties ('catalyst') in hydrogen, the material containing at least one metal selected from the group consisting of nickel, cobalt, iron, palladium, and platinum; at least one metal selected from the group consisting of chromium, molybdenum, tungsten, and uranium; and an active phase carrier. Downstream of the catalyst or mixed therewith is a mercury collecting material containing a sulfide of at least one metal selected from the group consisting of copper, iron, and silver or sulfur, and an active phase carrier.
Description
As everyone knows, the lime set by product of process gas (natural-gas, associated gas) and crude oil may contain multiple trace metal compound, they generally are the form of organometallic complex, wherein the carbon atom Cheng Jian in metal and the one or more organometallic group.
These metallic compounds are poisonous substances of the catalyzer that uses in petroleum conversion process.Specifically, owing to being deposited on the poisoning of catalyst that makes hydrofining and hydrogenation on the active surface gradually.Some metallic compounds especially are present in the heavy fraction of rectifying ship output oil in (nickel, vanadium, arsenic, mercury) or the gas reducing liquid (mercury, arsenic).
Above-mentioned hydrocarbon fraction is carried out thermally splitting or catalytic cracking processing, for example it is carried out steam cracking and is converted into lighter hydrocarbon fraction, can allow to remove some metal (as nickel, vanadium ...); In contrast, some other metal is (as mercury, arsenic ...) can generate volatile compound and/or be exactly volatile (mercury) in element state, they are present in the lighter fraction at least in part equally, and in fact can make the poisoning of catalyst of conversion process subsequently.And mercury has with aluminum base alloy for example and form amalgam and cause corrosive danger, and is especially low as to be enough to cause the technology section (deep cooling fractionation, heat exchanger) of liquid mercury condensation in those service temperatures.
It is known removing the mercury in the gas phase hydrocarbon or the method that has earlier of arsenic; People particularly operate in the presence of solids, can be indistinguishably with they called afters: sorbent material, collector, trapping agent, extraction agent, metal transfering agent etc.
For the method that relates to mercury removal agent:
United States Patent (USP) 3194629 has been narrated by being deposited on some solidss that sulphur on the activated carbon surface or iodine are formed.
The applicant's United States Patent (USP) 4094777 has been narrated other solidss, and they comprise to small part being copper and a kind of inorganic carrier of sulphided form.These solidss can contain silver equally.
The applicant's french patent application 87-07442 has narrated the method for the described solids of a kind of special preparation.
French Patent 2534826 has been narrated other solidss of being made up of elementary sulfur and inorganic carrier.
For the method that relates to dearsenification:
Patent DE2149993 has narrated use group VIII metal (nickel, platinum, palladium).
United States Patent (USP) 4069140 has been narrated the service condition of different sorbent materials.Narrate the ferric oxide that carrier is arranged, in United States Patent (USP) 3782076, narrated the use of plumbous oxide, and in United States Patent (USP) 3812653, narrated the use of cupric oxide.
Yet, good performance is arranged although more specifically say so for gas (as hydrogen) or mixed gas (as Sweet natural gas) when the demercuration or the dearsenification that contain in the Sweet natural gas when having hydrocarbon more than the carbon of three carbon or three in a large number at some product described in the prior art, but the experiment that the applicant did shows, in case material contains other compound that is not metal element, same product just shows relatively poor efficient, for example, for arsenic, it is the arsine that contains the above hydrocarbon chain of two carbon or two carbon, and for mercury, be the mercury compound that mercury methyl and other contain the above hydrocarbon chain of two carbon or two carbon, and may be to contain other non-metallic element (sulphur, nitrogen ...) mercury compound.
In addition, other experiment that the applicant carries out smoothly shows that when having sulphur to exist in the material, it will influence each other with the reactive metal element of dearsenification, and when these metallic elements when small part becomes sulfide, their are loss of activity significantly.
The objective of the invention is a kind of perhaps method of arsenic of mercury contained in hydrocarbon material that removes, it can remedy methodical deficiency earlier.
Another object of the present invention can remove mercury when also containing the sulphur of larger proportion in hydrocarbon material and perhaps equally also remove arsenic.So-called larger proportion is meant 0.005～3%(weight), 0.02～2%(weight particularly).
According to method of the present invention, the mixture of material and hydrogen is contacted with the catalyzer that the back with catalytic property can at random be referred to as the arsenic trapping agent, this catalyzer contains:
The metal M of-at least a chosen from Fe, cobalt, nickel, palladium and platinum.
-at least a metal the N that is selected from chromium, molybdenum, tungsten and uranium.
-perhaps a kind of active phase carrier based at least a porous, inorganic matrix, on material flow, be positioned at after the described catalyzer or with it blended be the mercury trapping agent, it contains sulphur and/or at least a at least a metallic sulfide and a kind of active carrier mutually that is selected from the metal of copper, iron and silver.
According to another kind of implementation method of the present invention, equally can be in thick material (before dearsenification) also can be at hydrogen with have the compound of adding sulphur in the material of handling in the presence of the arsenic trapping agent of catalytic property, as organic sulfide, in the presence of second bed, carry out demercuration then.
When material also contained arsenic, it was removed simultaneously.The most handy part is at least operated for the material of liquid.
Also be surprised to find that, in the presence of the arsenic of high density, and at high " liquid " per hour under the volumetric velocity, can cause having that incomplete arsenic captures (such as being lower than 90%) on the arsenic trapping agent of catalytic property, the function of mercury trapping agent is also as being gratifying to the arsenic trapping agent.
At last, also be surprised to find that, this catalyzer allows hydrogenating desulfurization, hydrodenitrification equally and the unsaturated compound that exists in material is proceeded to the hydrogenation of small part, and when described material is designated when carrying out steam cracking, this catalyzer can show superiority.At last, if when also having vanadium and/or nickel to exist except arsenic and mercury, described trapping agent can remove these metals effectively.
Be even that when not having described metal fully in the material, the catalytic property of described trapping agent still remains unchanged unexpectedly.
Therefore, described arsenic trapping agent with catalytic property is a kind of solid of complexity; When hydrogen exists and under operational condition as described below, it will
-by catalytic activation mercury and arsenic compound (if having arsenic to exist), and it is changed into the activated compound of trapping agent of the present invention,
-optionally capture arsenic (if having arsenic exist),
Even-when not having arsenic compound fully and exist, by the described mercury compound of catalytic activation.
Therefore, be added to the arsenic trapping agent of being appointed as " catalyzer " in the purpose composition of the present invention afterwards and contain the metal M and at least a metal N that is selected from chromium, molybdenum, tungsten and uranium of at least a chosen from Fe, nickel, cobalt, palladium, platinum with catalytic property, these metals exist with the form of oxide compound and/or oxysulfide and/or sulfide, and they can intactly use or preferably be deposited on the listed carrier at least a back.Under working conditions, it is the form that is in sulfide that metal M and/or metal N must have at least 50% of its total amount.
The professional knows that the equilibrium state between reduction form and the sulfur form depends on other operational condition, except temperature, and steam partial pressure in hydrogen partial pressure, hydrogen sulfide sectional pressure and the reaction medium particularly, such as:
The quantity separately of contained one or more metal M and one or more metals N generally is that to make the atomic ratio M/N of one or more metal M and one or more metals N be about 0.3: 1～about 0.7: 1 in catalyzer, is preferably about 0.3: 1～about 0.45: 1.
Contained weight metal is expressed as the ratio of weight of the weight finished catalyst of metal in finished catalyst, and for one or more metals N, this value is generally about 2～30%, be preferably about 5～25%, for one or more metal M, be about 0.01～15%, more preferably about 0.01～5% for palladium and platinum, be preferably about 0.05～3%, and for base metal M(Fe, Co, Ni), be generally approximately 0.5～15%, be preferably about 1～10%.
In metal N, preferably use molybdenum and/or tungsten, and in metal M, preferably use base metal iron, cobalt and/or nickel.Preferably use following metallic combination: nickel-molybdenum, nickel-tungsten, cobalt-molybdenum, cobalt-tungsten, iron-molybdenum and iron-tungsten.Best combination is nickel-molybdenum and cobalt-molybdenum.Equally also can use the combination of three kinds of metals, as nickel-cobalt-molybdenum.
Selecting the porous, inorganic matrix is in order to make final catalyzer have optimum pore volume performance.This matrix generally contains at least a following material: aluminum oxide, silicon oxide, silica-alumina, magnesium oxide, zirconium white, titanium oxide, clay, high-alumina cement, aluminate class is as magnesium aluminate, calcium aluminate, strontium aluminate, barium aluminate, manganese aluminate, iron aluminate could, Leyden blue, nickel aluminate, cupric aluminate and Zinc aluminate, aluminate mixture for example contains the aluminate mixture of at least two kinds of above-mentioned metals.
May more wish to use and contain aluminum oxide for example aluminum oxide and silica-alumina or also contain the matrix of titanium oxide.When matrix contained silicon oxide, the amount of silicon oxide preferably accounted for the matrix gross weight and mostly is 25% most.
Except at least a above-claimed cpd, described matrix can contain at least a synthetic or natural zeolites aluminum oxide-silicate crystal (zeolite) equally.The amount of zeolite generally accounts for 0～95%(weight of matrix gross weight), be preferably 1～80%(weight).
Can also advantageously use the mixture of aluminum oxide and zeolite or the mixture of silica-alumina and zeolite.
In the middle of zeolite, Siliciumatom is higher than about 5: 1 zeolite with the ratio (Si/Al) of aluminium atom on the general hope use matrix.It is favourable using the zeolite and the particularly stabilized or hyperstabilized Y zeolite of faujusite structure.
The matrix of normal use is an aluminum oxide, and generally more wishes to use pure or blended transitional alumina, for example γ
C, γ
T, δ, θ.
Described matrix preferably will have big surface-area and enough pore volumes, in other words, be respectively 50 meters at least
2/ restrain and 0.5 centimetre
3/ gram, for example 50～350 meters
2/ restrain and 0.5～1.2 centimetre
3/ gram.At least equal the shared ratio of macropore that 0.1 micron hole constitutes together by mean diameter and will account for 10～30% of total pore volume.
The method for making of this catalyzer is that the professional knows, and no longer repeats within the scope of the invention.
If necessary, before using, described catalyzer can be handled under 50～500 ℃ temperature with the gas that contains hydrogen.If necessary, it equally can be at least in part for example by French SULFICAT(R) method or carry out prevulcanized by in the presence of hydrogen sulfide and/or other sulfide, handling.
The mercury trapping agent that adds in purpose composition of the present invention is made up of the sulphur or the sulfide that are deposited on carrier or the porous, inorganic matrix, and the porous, inorganic matrix is selected from aluminum oxide, silica-alumina, silicon oxide, zeolite, clay, activated carbon, high-alumina cement, titanium oxide, zirconium white or is selected from addition described other carrier that is made of the porous, inorganic matrix of catalyzer.
As trapping agent, can use the sulphur that is deposited on the carrier and, more in general, can use all products of forming as at the sulphur described in the French Patent 2534826 by being deposited on the activated carbon or on the macroporous aluminium oxide as the commodity of GALGON HGR and so on.
Preferably use the compound that contains sulphur and a kind of metal P, P is selected from copper, iron, silver herein, and as preferred mode, can be the combination of copper or copper-Yin.Have at least 50% metal P to use with the form of sulfide.
The method of being recommended in can United States Patent (USP) 4094777 according to the applicant, or deposited copper oxide is vulcanized with the organic polysulfide described in the applicant's the french patent application 87/07442 then and is prepared this trapping agent on aluminum oxide.
The bonded in trapping agent or the ratio of uncombined elementary sulfur are 1～40% more favourable, and preferred mode is in 1～20%(weight).
Be the bonded of sulphided form or the ratio of uncombined metal P and be preferably 0.1～20% of trapping agent gross weight.
The composition of being made up of catalyzer and mercury trapping agent can use in two reactors and also can use in single reactor.
When using two reactors, they can be connected, and the reactor that catalyzer is housed preferably is placed on before the reactor that trapping agent is housed.
When using single reactor, catalyzer and trapping agent can be placed on two isolating beds, also can closely mix placement.
Amount (pressing element form calculates) according to mercury and/or arsenic contained in the material has the arsenic trapping agent of catalytic property and the volume ratio of mercury trapping agent and can be 1: 10 to 5: 1.
When the isolating reactor of operation, the reactor that the arsenic trapping agent with catalytic property is housed can be at 180～450 ℃, more preferably 230～420 ℃, are preferably 260～390 ℃ the interior operation of temperature range.
Working pressure is selected from and is preferably 1～50 crust (absolute pressure), particularly 5～40 cling to, best to be 10～30 crust rise the hydrogen flowing quantity that number (normal temperature, normal pressure) represents with the hydrogen of every liter of liquid material is preferably between 1～1000, particularly between 10～300.Best is to select between 30～200.
Can be with respect to hour volumetric velocity that the arsenic trapping agent with catalytic property calculates at 0.1-30 hour
-1, particularly 0.5～20 hour
-1, best is 1～10 hour
-1(every volume arsenic trapping agent liquid volume hourly).
The mercury trapping agent will be more preferably 20～350 ℃ at 0～400 ℃, preferably operation in 40～330 ℃ the temperature range.
Working pressure and hydrogen flowing quantity D will be determined by the arsenic trapping agent with catalytic property.
Hour volumetric velocity of calculating with respect to the mercury trapping agent can be for the arsenic trapping agent with catalytic property pointed, certainly as noted earlier, the volume ratio of arsenic trapping agent and mercury trapping agent is 1: 10 to 5: 1, and this will depend on the arsenic in the material and the ratio of mercury especially.Therefore, apparent, the relative proportion of two kinds of trapping agents, thereby just with respect to the latter's hour volumetric velocity at this moment can differ widely (that is to say liquid flow rate identical and trapping agent volume difference).
In one embodiment of the invention,, before passing through on the mercury trapping agent, perhaps can be cooled at handled material in the presence of the catalyzer.
In another scheme, two kinds of trapping agents are placed in the same reactor, can be more preferably 190～350 ℃ at 180～400 ℃, preferably this reactor of operation in 200～330 ℃ the temperature range.
At last, as known to the professional, after separating the liquid product of purifying, from the beginning, the hydrogen-rich gas that recycles recovery at least partially may be good.Except the consumption that reduces hydrogen greatly, described circulation can be controlled the intrinsic standoff ratio pH in the reaction medium better
2S/pH
2Just as noted earlier, and when material contains a small amount of sulphur [for example be less than 20ppm(weight)], in material and/or hydrogen, add at least a sulfide, for strengthening described pH
2S/pH
2Than other benefit can be arranged.
In being particularly suitable for material of the present invention, every kilogram of material contains 10
-3～2 milligrams of mercury, perhaps every kilogram of material also contains 10
-2～10 milligrams of arsenic.
Following each example can be used to illustrate different aspect of the present invention and does not limit its scope.Concerning the professional, it is evident that, in view of these examples, if handle only arsenical material, so only just enough with the arsenic trapping agent, otherwise,, just must use mercury trapping agent and arsenic trapping agent with catalytic property as if the mercury that will remove effectively in the only mercurous material.Represented contrast experiment carries out in the material that is not having arsenic to exist in example 1 to 4.They have similar result.
Example 1(contrast)
In the steel reactor of 3 centimetres of diameters, add 250 centimetres
3Catalyzer HR306, the product of RROCATALYSE.
Described catalyzer HR306 is by 1.2 millimeters of diameters, long 2 to 10 millimeters, contains cobalt 2.36%(weight), molybdenum 9.35%(weight) the extruding granulometric composition, matrix is made of transitional alumina.Specific surface is 210 meters
2/ gram, pore volume is 0.48 centimetre
3/ gram.
Then this catalyzer being carried out prevulcanized handles.Injecting volume ratios according to 10 liters/hour amounts is 3: 97 H
2S-H
2Mixed gas.Heat-up rate is 1 ℃/minute, at last 350 ℃ of constant temperature 2 hours.
The flow that only keeps hydrogen, last heavy lime set of liquefied gas (its character is as pointed in the table I) and the hydrogen that on catalyzer, passes through upwelling, condition is as follows:
Mass flow: 500 centimetres
3/ hour
Temperature: 320 ℃
Stagnation pressure: 30 ℃ (absolute pressure)
Hydrogen flowing quantity: 100 liters/rise material, promptly 50 liters/hour.
Logical lime set and hydrogen 500 hours, at 20,50,100,200 and 500 hours not mercury in the analysed preparation and arsenic the results are summarized in the table III.
As can be seen, this catalyzer shows very poor efficient for capturing mercury, for capturing arsenic good efficient is arranged then on the contrary.
Example 2(contrast)
In this example, prepared the trapping agent that constitutes by sedimentary cupric sulfide on the alumina supporter of narration in the applicant's United States Patent (USP) 4094777.
This trapping agent contains and is the 12%(weight that sulphided form exists) copper and 6%(weight) sulphur.Matrix is made up of transitional alumina.Specific surface is 70 meters
2/ gram, 0.4 centimetre of pore volume
3/ gram.
With reactor identical described in the example 1 in add 100 centimetres
3This trapping agent.To pass through (referring to the table I) with rising liquid stream on trapping agent with the heavy lime set of used identical liquefied gas in the example 1 then, condition is as follows:
Mass flow: 500 centimetres
3/ hour
Stagnation pressure: 30 crust (absolute pressure)
Temperature: 40 ℃
Hydrogen flowing quantity: 100 liters/rise material, promptly 50 liters/hour.
Logical lime set 500 hours was not shown in the III the results are summarized in of mercury in the product and arsenic analysis at 20,50,100,200 and 500 hours.
We see that trapping agent is inefficent for capturing arsenic.On the contrary, to capturing mercury of short duration efficient is arranged, but this efficient descends soon in time.
Example 3(contrast)
Repeat the experiment in the example 2, but obstructed hydrogen.
The result that the table III provides shows that its performance is not improved.
Example 4(is according to the present invention)
Be used in technology described in the example 1 and pretreatment process, in first reactor, add 250 centimetres
3Example 1, catalyzer HR306 carry out pre-treatment then.
In second reactor, according to adding 100 centimetres in the technology described in the example 2
3The trapping agent of example 2.
Under hydrogen, feed the liquefied gas heavy lime set identical in the mode of upwelling, make it on catalyzer and trapping agent, to pass through successively with example 1.
Operational condition is as follows:
Mass flow: 500 centimetres
3/ hour
Catalyzer HR300:250 centimetre
3
Temperature: 320 ℃
Stagnation pressure: 30 crust (absolute pressure)
Hydrogen flowing quantity: 100 liters/rise material, promptly 50 liters/hour.
Cupric sulfide trapping agent: 100 centimetres
3
Temperature: 40 ℃
Stagnation pressure: 30 crust (absolute pressure)
Hydrogen flowing quantity: 100 liters/rise material, promptly 50 liters/hour.
Logical lime set reaches 1000 hours, in the 50th, 100,200,500,1000 hour last analysed preparation in the table IV that the results are summarized in the back of mercury.
Be surprised to find that the combination of catalyzer HR306 and trapping agent can obtain the high arsenic-removing rate and the demercuration rate of lime set.
To the analysis revealed of catalyzer HR306, the fixed arsenic more than 90% is arranged in described catalyzer; On the contrary, the concentration of mercury then is lower than 20ppm(weight).And to the analysis revealed of mercury trapping agent, it is actual contains 100% mercury and is less than 10% fixed arsenic.
These master metal will be preceding 50 centimetres of bed
3In.Therefore estimating to have the very long life-span.
Example 5(is according to invention)
In order to represent the anti-sulphur of catalyst system, in example 1, replenish 0.5%(weight in the handled material) be the sulphur of thiophene form.
It is identical that operational condition keeps, and just the service temperature of catalyzer HR306 brought up to 340 ℃, hydrogen flowing quantity bring up to 200 liters/rise material, promptly 100 liters/hour.
In analysis precision, the table performance that III gathered is identical.
Example 6(is according to the present invention)
Repeat the experiment described in the example 4.Be equipped with 100 centimetres
3Contain in the reactor of trapping agent of the copper that liquefies and be equipped with:
100 centimetres
3Described trapping agent and
50 centimetres
3The mercury trapping agent, it is according to the method described in the United States Patent (USP) 3194629 preparation, contains 13%(weight on CALGON HGR type gac) sulphur.
Other operational condition is still strict identical, and experiment is limited to 500 hours.
The multiple experimental result shows that the mercury removal agent that is added on the gac improves to some extent the demercuration performance in the table III.Otherwise the dearsenification performance is constant.
Example 7(is according to the present invention)
Still be equipped with 200 centimetres in first reactor that in example 3, uses
3Catalyzer HMC841 by the PROCATALYSE sale.
This catalyzer is that diameter is 1.5～3 millimeters a bead, contains 1.96%(weight) nickel and 8%(weight) molybdenum; Matrix is made of transitional alumina.Specific surface is 140 meters
2/ gram, pore volume is 0.89 centimetre
3/ gram.According to the business-like SULFICAT(R of EURECAT company) technology, with this catalyzer HMC841 prevulcanized (vulcanization in situ), its sulphur content reaches 4.8%(weight before reinforced).
Add 200 centimetres in second reactor
3The mercury trapping agent, it is by the described methods preparation of the applicant's United States Patent (USP) 4094777, contain 8%(weight) sulphur, 14.5%(weight) copper and 0.2%(weight) silver, according to the method described in the applicant's the French Patent 87-07442, carry out prevulcanized then by contacting with a kind of organic polysulfide.
The performance of handled new material (the heavy lime set of liquefied gas) is as showing shown in the II test period 1000 hours.
Predetermined operational condition is as follows:
Mass flow: 0.6 liter/hour
Catalyzer HMC841:200 centimetre
3
Temperature: 390 ℃
Pressure: 40 crust
Hydrogen flowing quantity: 150 liters/rise material, promptly 90 liters/hour.
The trapping agent of Containing Sulfur copper and silver sulfide: 200 centimetres
3
Temperature: 100 ℃
Pressure: 40 crust
The 20th, 50, the analytical results of mercury and arsenic is summarised in the table III in 100,200,500 and 1000 hours foot couple products.We see that the dearsenification of material always remains on more than 99%, and demercuration always remains on more than 98.8%.
In addition, analyze demonstration at the liquid stream that the 500th hour foot couple of experiment purified, it only contains 60ppm(weight) sulphur and 33ppm(weight) nitrogen.Therefore, hydrogenating desulfurization rate and hydrodenitrification rate are respectively 95.4% and 24%.On the other hand, materials flow only contains 28% aromatic hydrocarbons (comparing with 41% in the fresh material), this shows that except dearsenification and demercuration activity were arranged, composition of the present invention (catalyzer+mercury trapping agent) also had the performance of additional hydrogenating desulfurization, hydrodenitrification and aromatic hydrogenation.
Example 8(is according to the present invention)
Handled material is still described in the table II.
The use diameter is 4 centimetres a single reactor now, is equipped with to the exit from inlet:
Press the catalyzer HMC841 of example 7 prevulcanized outside reflecting point 0.5 rise,
0.2 rise the Containing Sulfur copper and the silver sulfide trapping agent that in example 7, use.
Service temperature equals 200 ℃, working pressure equal 50 the crust (absolute pressure), flow be 200 liters/rise material, promptly 120 liters/hour.
Mass flow is 0.6 liter/hour.
Separate after the material of (high-pressure separator) purification, to the analysis revealed that the hydrogen that reclaims from outlet carries out, it contains hydrogen sulfide, and this carries out hydrogenating desulfurization by described material and forms in the presence of catalyzer HMC841.
Test period 500 hours, the performance that obtains are summarized in the table III.
Can see, in a reactor, use two kinds of catalyzer, produce good result for material demercuration and dearsenification.
The table I
The material performance of example 1 to 6
Pore volume 0.754 g/cm
3
S(weight) 150
Hg(weight) 0.6
As(weight) 0.5
Pi 22
Distill 5% 35
ASTM D 86 50% 129
（℃） 95 330
Final boiling point 475
The table II
Example 7 and 8 material performance
Pore volume 0.769 g/cm
3
S(weight) 1300
N(weight) 45
Hg(weight) 1.1
As(weight) 1.5
Fe(weight) 1
Aromatic hydrocarbons (% weight) 41
Pi 30
Distill 5% 42
ASTM D 86 50% 127
（℃） 95 362
Final boiling point 497
The table III
As Hg As Hg As Hg
Instance number
C% ppb C% ppb C% ppb C% ppb C% ppb C% ppb
Experimental period 20 hours 50 hours 100 hours
1 99 5 20 480 99 5 15 510 98 10 14 517
2 10 450 97 18 8 460 95，5 28 7 465 88 71，5
3 9 455 96 24 9 455 96 24 8 460 87 78
4 99 5 97 18 98，5 7，5 98 12 99 5 97 17
5 99 5 97，5 14 99 5 98 11 98，5 7，5 97，5 15
6 98 10 98，2 11 99 5 98，5 9 99 5 98 12
7 99，5 7，5 98，9 12 99，3 10 99 11 99，4 9 99 11
8 99，3 10 98，5 16 99 15 99，5 6 99，1 13 99，4 7
Table III (continuing)
As Hg As Hg As Hg
Instance number
C% ppb C% ppb C% ppb C% ppb C% ppb C% ppb
Experimental period 200 hours 500 hours 1000 hours
1 99 5 12 530 99 5 10 540
2 8 460 53 282 5 475 31 415
3 7 465 54 277 6 470 30 420
4 98 10 98 11 99 5 97，5 15 98，5 7，5 98 12
5 98 10 97，5 14 99 5 98 12 99 5 97，5 14
6 98，5 8 98，3 10 99 5 98，8 7，2
7 99，3 11 99，1 10 99，3 10 98，9 12 99，2 12 98,8 13
8 99 15 99，3 8 98，9 16 99，3 8
C%=to the fixed rate of mercury and arsenic, represents with weight percentage on the composition of being made up of catalyzer and mercury trapping agent.
The residual concentration of ppd=arsenic and mercury is with microgram (10
-6Gram)/kilogram or the expression of milligram/ton.
Claims (16)
1, remove and contain mercury, the mercury in the hydrocarbon material of arsenic and element sulphur and the method for arsenic, it is characterized in that, in the presence of arsenic trapping agent, the mixture of hydrogen and described material is reacted with catalytic property, described " catalyzer " contains at least a nickel that is selected from, cobalt, iron, the metal M of palladium and platinum, at least a chromium that is selected from, the metal N of molybdenum and tungsten, and perhaps at least a active phase carrier based at least a porous, inorganic matrix, on material flow, be positioned at described have the arsenic trapping agent back of catalytic property or with it blended be the mercury trapping agent, the mercury trapping agent contains a kind of copper that is selected from least, sulfide or sulphur and a kind of active carrier of a kind of metal P of iron and silver.
2, according to the method for claim 1, according to the method, removing mercury metal and arsenic simultaneously, material is equally partly by hydrogenating desulfurization, hydrodenitrification and to its unsaturated hydrocarbon moiety hydrogenation.
3, according to the process of claim 1 wherein, in material, perhaps also replenish at least a sulfide that is selected from hydrogen sulfide and organic sulfide.
4, according to the process of claim 1 wherein that catalyzer contains 0.01～15%(weight) at least a metal M, 2～30%(weight) at least a metal N, and the atomic ratio of M/N is 0.3: 1～0.7: 1 herein.
5, according to the process of claim 1 wherein that metal M is cobalt and nickel, metal N is molybdenum and tungsten, and catalyzer contains 0.5～15%(weight herein) at least a metal M, 5～25%(weight) at least a metal N.
6, according to the process of claim 1 wherein, catalyzer contains at least a precious metal that is selected from palladium and platinum in metal M, and catalyzer described herein contains 0.01～5% metal M.
7, according to the method for claim 1, wherein, except metal M and N, catalyzer also contains the active phase carrier that is made of the porous, inorganic matrix, and this porous, inorganic matrix contains at least a compound that is selected from aluminum oxide, silicon oxide, silica-alumina, magnesium oxide, zirconium white, titanium oxide, clay, high-alumina cement, aluminate, the synthetic or natural zeolite class pure aluminium silicate.
8, according to the process of claim 1 wherein that the mercury trapping agent comprises 1～40% sulphur and at least a carrier that is selected from aluminum oxide, silica-alumina, silicon oxide, titanium oxide, zirconium white, zeolite, gac, clay and high-alumina cement that accounts for its gross weight.
9, according to the process of claim 1 wherein that the mercury trapping agent also contains 0.1～20%(weight) at least a metal P that is selected from copper, iron and silver, and metal P is the form of sulfide at least in part herein.
10, according to the process of claim 1 wherein:
-working pressure is selected in 1～50 crust (absolute pressure)
-hydrogen flowing quantity is selected in 1～1000 liter of (standard state) hydrogen/rise liquid material
-per hour the volumetric velocity represented with the liquid material volume is per unit volume catalyzer 0.1～30 volume, and per unit volume mercury trapping agent 0.1～30 volume
-catalyzer service temperature is 180～450 ℃
-mercury trapping agent service temperature is 0～400 ℃
-catalyzer and mercury trapping agent are placed in two reactors that separate, and material contacts with catalyzer earlier to capture with mercury then and contacts.
11, according to the method for claim 10, wherein
-catalyzer and mercury trapping agent are placed in the single reactor, and the service temperature in the reactor is 180～400 ℃.
12, according to the method for claim 10, wherein hydrogen-rich gas is separated from the overhead product of one or several reactor, circulated from the beginning of first reactor at least in part then.
13, with containing at least a mixed gas that is selected from the compound of hydrogen, hydrogen sulfide and organic sulfide catalyzer is carried out pre-treatment down at 50～500 ℃ earlier according to the process of claim 1 wherein, and then the handle hydrocarbon material.
14, according to the process of claim 1 wherein that every kilogram of material contains 10 by being the material of the hydrocarbon composition of liquid to small part at normal temperatures and pressures
-3～2 milligrams of mercury, perhaps every kilogram of material contains 10
-2～10 milligrams of arsenic.
15, according to the method one of in the claim 1 to 14, heavy material or overhead product that wherein handled material is thermal transition and/or catalytic conversion process.
16, according to the method one of in the claim 1 to 14, wherein handled material is the lime set of gas.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR89/03.581 | 1989-03-16 | ||
| FR8903581A FR2644472B1 (en) | 1989-03-16 | 1989-03-16 | PROCESS FOR THE REMOVAL OF MERCURY AND POSSIBLY ARSENIC IN HYDROCARBONS |
| FR8903581 | 1989-03-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1045596A CN1045596A (en) | 1990-09-26 |
| CN1024675C true CN1024675C (en) | 1994-05-25 |
Family
ID=9379843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90101386A Expired - Lifetime CN1024675C (en) | 1989-03-16 | 1990-03-16 | Process for removing mercury or arsenic from hydrocarbons |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0463044B1 (en) |
| JP (1) | JP2620811B2 (en) |
| CN (1) | CN1024675C (en) |
| AU (1) | AU634763B2 (en) |
| CA (1) | CA2012344C (en) |
| DE (1) | DE69002941T2 (en) |
| DZ (1) | DZ1402A1 (en) |
| FR (1) | FR2644472B1 (en) |
| MY (1) | MY106411A (en) |
| NO (1) | NO180121C (en) |
| WO (1) | WO1990010684A1 (en) |
| ZA (1) | ZA893265B (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2666343B1 (en) * | 1990-08-29 | 1992-10-16 | Inst Francais Du Petrole | PROCESS FOR REMOVAL OF MERCURY FROM VAPOCRACKING PLANTS. |
| FR2668465B1 (en) * | 1990-10-30 | 1993-04-16 | Inst Francais Du Petrole | PROCESS FOR REMOVAL OF MERCURY OR ARSENIC IN A FLUID IN THE PRESENCE OF A MASS OF MERCURY AND / OR ARSENIC CAPTATION. |
| FR2668385B1 (en) * | 1990-10-30 | 1993-10-15 | Institut Francais Petrole | PROCESS FOR THE ELIMINATION OF ARSENIC IN A GAS BY PASSING ON A MASS BASED ON A SUPPORT OF COPPER SULFIDE. |
| US5085844A (en) * | 1990-11-28 | 1992-02-04 | Phillips Petroleum Company | Sorption of trialkyl arsines |
| US5064626A (en) * | 1990-11-28 | 1991-11-12 | Phillips Petroleum Company | Trialkyl arsine sorbents |
| FR2673191B1 (en) * | 1991-02-27 | 1994-02-04 | Institut Francais Petrole | PROCESS FOR REMOVING MERCURY AND / OR ARSENIC FROM THE LOADS OF SOLVENT DEAROMATIZATION UNITS. . |
| FR2673192B1 (en) * | 1991-02-27 | 1994-07-22 | Inst Francais Du Petrole | PROCESS FOR THE ELIMINATION OF MERCURY AND POSSIBLY ARSENIC IN THE LOADS OF CATALYTIC PROCESSES PRODUCING AROMATICS. . |
| FR2690923B1 (en) * | 1992-05-11 | 1994-07-22 | Inst Francais Du Petrole | PROCESS FOR CAPTURING MERCURY AND ARSENIC IN A CUP OF HYDROCARBON. |
| FR2698372B1 (en) * | 1992-11-24 | 1995-03-10 | Inst Francais Du Petrole | Process for the removal of mercury and possibly arsenic from hydrocarbons. |
| FR2701270B1 (en) * | 1993-02-08 | 1995-04-14 | Inst Francais Du Petrole | Process for removing mercury from hydrocarbons by passing over a presulfurized catalyst. |
| FR2701269B1 (en) * | 1993-02-08 | 1995-04-14 | Inst Francais Du Petrole | Process for the elimination of arsenic in hydrocarbons by passage over a presulfurized capture mass. |
| US6350372B1 (en) * | 1999-05-17 | 2002-02-26 | Mobil Oil Corporation | Mercury removal in petroleum crude using H2S/C |
| FR2803597B1 (en) | 2000-01-07 | 2003-09-05 | Inst Francais Du Petrole | PROCESS FOR CAPTURING MERCURY AND ARSENIC FROM A DISTILLED HYDROCARBON CUT |
| JP2002241767A (en) * | 2001-02-15 | 2002-08-28 | Idemitsu Petrochem Co Ltd | Method for removing mercury from liquid hydrocarbon |
| CN100392046C (en) * | 2003-08-07 | 2008-06-04 | 上海化工研究院 | Dearsenicating agent for removing high boiling point arsonium compound in liquid-state petroleum hydrocarbon at low temperature and normal temperature |
| GB0611316D0 (en) * | 2006-06-09 | 2006-07-19 | Johnson Matthey Plc | Improvements in the removal of metals from fluid streams |
| CN101970614A (en) * | 2008-03-10 | 2011-02-09 | 巴斯夫欧洲公司 | Method for removing mercury from hydrocarbon streams |
| KR101796792B1 (en) * | 2011-02-09 | 2017-11-13 | 에스케이이노베이션 주식회사 | A method for simultaneous removing of sulfur and mercury in hydrocarbon source comprising them using catalyst through hydrotreating reaction |
| FR2987368B1 (en) * | 2012-02-27 | 2015-01-16 | Axens | PROCESS FOR REMOVING MERCURY FROM HYDROCARBON LOAD WITH HYDROGEN RECYCLE |
| CN104507551B (en) * | 2012-08-20 | 2018-08-07 | 艺康美国股份有限公司 | Mercury absorbent |
| FR3007415B1 (en) * | 2013-06-21 | 2016-05-27 | Ifp Energies Now | PROCESS FOR REMOVING THE ARSENIC FROM A HYDROCARBON LOAD |
| CN104645927B (en) * | 2013-11-25 | 2018-01-16 | 北京三聚环保新材料股份有限公司 | A kind of preparation method of silver system mercury removal agent |
| CN108456574A (en) * | 2018-04-12 | 2018-08-28 | 西南石油大学 | A kind of mercury removal agent and preparation method thereof for moisture demercuration |
| CN114073961A (en) * | 2021-12-08 | 2022-02-22 | 辽宁石油化工大学 | Cr-Cu/SiO with dearsenization performance2Process for preparing catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3110569A (en) * | 1958-02-05 | 1963-11-12 | Socony Mobil Oil Co Inc | Removal of arsenic from reformer feed |
| US4069140A (en) * | 1975-02-10 | 1978-01-17 | Atlantic Richfield Company | Removing contaminant from hydrocarbonaceous fluid |
| US4474896A (en) * | 1983-03-31 | 1984-10-02 | Union Carbide Corporation | Adsorbent compositions |
| US4709118A (en) * | 1986-09-24 | 1987-11-24 | Mobil Oil Corporation | Removal of mercury from natural gas and liquid hydrocarbons utilizing downstream guard chabmer |
-
1989
- 1989-03-16 FR FR8903581A patent/FR2644472B1/en not_active Expired - Lifetime
- 1989-05-03 ZA ZA893265A patent/ZA893265B/en unknown
- 1989-07-18 JP JP1185823A patent/JP2620811B2/en not_active Expired - Lifetime
-
1990
- 1990-02-28 DZ DZ900038A patent/DZ1402A1/en active
- 1990-03-09 DE DE90904870T patent/DE69002941T2/en not_active Expired - Fee Related
- 1990-03-09 EP EP90904870A patent/EP0463044B1/en not_active Expired - Lifetime
- 1990-03-09 AU AU53319/90A patent/AU634763B2/en not_active Ceased
- 1990-03-09 WO PCT/FR1990/000162 patent/WO1990010684A1/en active IP Right Grant
- 1990-03-13 MY MYPI90000396A patent/MY106411A/en unknown
- 1990-03-16 CN CN90101386A patent/CN1024675C/en not_active Expired - Lifetime
- 1990-03-16 CA CA002012344A patent/CA2012344C/en not_active Expired - Fee Related
-
1991
- 1991-09-13 NO NO913622A patent/NO180121C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0463044B1 (en) | 1993-08-25 |
| CN1045596A (en) | 1990-09-26 |
| NO913622D0 (en) | 1991-09-13 |
| EP0463044A1 (en) | 1992-01-02 |
| CA2012344C (en) | 2001-05-08 |
| NO913622L (en) | 1991-09-13 |
| CA2012344A1 (en) | 1990-09-16 |
| AU634763B2 (en) | 1993-03-04 |
| NO180121B (en) | 1996-11-11 |
| JP2620811B2 (en) | 1997-06-18 |
| DZ1402A1 (en) | 2004-09-13 |
| FR2644472B1 (en) | 1991-06-21 |
| MY106411A (en) | 1995-05-30 |
| NO180121C (en) | 1997-02-19 |
| JPH02248493A (en) | 1990-10-04 |
| FR2644472A1 (en) | 1990-09-21 |
| DE69002941T2 (en) | 1993-12-23 |
| AU5331990A (en) | 1990-10-09 |
| DE69002941D1 (en) | 1993-09-30 |
| WO1990010684A1 (en) | 1990-09-20 |
| ZA893265B (en) | 1990-04-25 |
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Granted publication date: 19940525 |