CN1100123C - Method of removing iron from petroleum fraction - Google Patents

Abstract

The present invention discloses a method for removing iron in petroleum distillate, which comprises that ferrous petroleum distillate is in contact with an inert fibrous material bed in hydrogen atmosphere under the conditions of the contact temperature of 150 to 450 DEG C, the hydrogen partial pressure of 0.1 to 20MPa, the volume ratio of hydrogen oil of at least 50 and the weight space velocity of 1 to 30 hours<-1>. Compared with the prior art, the method of the present invention has a higher iron removal rate at the same or lower temperature.

Description

A kind of method that removes the iron in the petroleum fractions

The invention relates to a kind of heteroatomic method of removing in the petroleum fractions, the method for more specifically saying so and removing the iron in the petroleum fractions about a kind of.

Often contain metallic impurity in the petroleum fractions, when wherein content of acidic compounds more for a long time, in the process of processing petroleum fractions, these acidic cpds also can corrode transport pipe or reactor, and the metals content impurity in the oil product is further raise.These metallic impurity generally are iron, vanadium, nickel, sodium, calcium etc., they can be with inorganic metal compound, form as metal oxide, metallic sulfide exists, also can be with organometallic compound, as the form existence of porphyrin thing, naphthenate and various derivatives thereof.In the course of processing of oil product, these metallic impurity, especially iron cpd easily form settling, are deposited in the space of catalyst particles intergranular, and the tamper circulation road sharply increases bed layer pressure.

And in recent years, the amount of finish of crude oil with poor quality increases day by day, meanwhile, the requirement of petroleum products quality is but improved constantly.Hydrogenation technique, as hydrocracking, hydrotreatment, hydro-upgrading, hydrofining, to face technology such as hydrogen dewaxing be the processing inferior feedstock oil, one of effective means of improving the quality of products, the existence of iron contamination has brought adverse influence for equally above-mentioned hydrogenation technique process in the stock oil, therefore, the iron in the stock oil must be removed.

Remove the existing report of method of iron contamination in the stock oil, as US3,573,201 disclose a kind of method that removes the iron contaminants that exists as the solubility organic compound that contains in the hydrocarbon raw material, it is included under 400-1000 the temperature, described hydro carbons is passed through a container with hydrogen, this container only contains one and independently contacts particle layers, described contact particle contains at least a heat-resistant inorganic oxide, described metal deposition is on the contact particle layers, and its improvement is the bed form filling of described particle by slenderness ratio 0.20 at least.Suitable contact particle comprises aluminum oxide, silica-alumina, activated carbon and various mixed oxide.

US3,947,347 disclose a kind of method that removes ferrous contaminants from hydrocarbon raw material, be included in hydrogen and exist down, described hydrocarbon raw material is contacted with a kind of solid, described solid is made up of the inert particulate solid support material basically, this solid support material contains porose, and has 1-20m ²The specific surface of/g, described hole has the average pore diameter of 1000-10000 dust, and described material can contain or not contain hydrogenation component as the filling of contact material bed.Described contact conditions is, temperature 500-850 °F, pressure 300-3000Psig, liquid hourly space velocity 0.2-10, described hydrocarbon raw material is selected from by the crude oil of metallic pollution, topped crude or atmospheric residue, one group of forming of solvent-deasphalted oils, shale oil, coal tar and sand oil (Sand Oil), described inert material comprises the diatomite after corundum, aluminum oxide, the high-temperature roasting etc.

The solid particulate that the used deferrization material of two kinds of methods recited above all is moulding, as silicon oxide, aluminum oxide, diatomite etc., for improving deferrization efficient, sometimes also need be on these solid particulates the load hydrogenation component, as components such as nickel, cobalt, molybdenum, tungsten, the price of these solid particulates is more expensive, and in general the price with Primary Catalysts is suitable.In addition, these solid particulates are iron contaminations of relying on its duct to hold deposit, and the saturation in its duct is limited, and the space between the interior solid particulate of bed is also less, and voidage is lower.Therefore, metal deposit still can be deposited on the bed ingress very soon, causes pressure drop to raise.

US4,933,071 discloses a kind of method that removes iron from hydrocarbon raw material, be included in do not have under the condition that outer hydrogenation exists with 250-600 ℃ of temperature under, with described raw material by a kind of solid, inert filamentary material in a low pressure demetalization reaction zone, wherein, in the presence of described filamentary material, described iron and sulphur or sulfocompound reaction generate iron sulphide, the iron sulphide that generates is deposited on the described filamentary material, and further be deposited on iron sulphide originally on one's body.Described filamentary material can be glass yarn, rock wool, charcoal fiber etc.This method is to utilize iron sulphide that the mechanism of extensional mode self-catalyzed deposition takes place on fibrous matter, iron sulphide is deposited on the fibrous matter, and and then iron sulphide that the back is generated be deposited on the iron sulphide that is deposited on previously on the fibrous matter, adopt this method to the raw material (as the about 100ppm of iron level) of high Fe content when carrying out deferrization, the deferrization rate can reach 90%, but remaining iron level still higher (as being not less than 10ppm), such deferrization rate is still lower, can't alleviate the problem that the hydrogenation unit pressure drop raises rapidly at all.

The purpose of this invention is to provide the higher method that removes iron in the petroleum fractions of a kind of deferrization rate.

Method provided by the invention comprises a kind of iron content petroleum fractions is contacted with a kind of inert fiber shape material bed that wherein, described contact is to carry out under nitrogen atmosphere.The contact temperature is 150-450 ℃, and the hydrogen dividing potential drop is the 0.1-20 MPa, and hydrogen to oil volume ratio is at least 50, and weight hourly space velocity is 1-30 hour ^-1

According to method provided by the invention, described inert fiber shape material can be any under described reaction conditions infusible inert fiber material.Preferred inert fiber material comprises one or more in glass fibre, charcoal fiber, rock wool, the silica wool, wherein glass fibre more preferably.The mean diameter of described inert fiber material should be not more than 50 microns, preferably is not more than 20 microns, and thinner filamentary material has bigger specific surface, can hold above more iron sulphide is deposited on.The volume packing density of inert fiber bed is generally 2-15%, is preferably 5-10%.

According to method provided by the invention, described iron content petroleum fractions is selected from various mineral hydrocarbon oil, as being selected from crude oil, various distillates, solvent-refined oil, solvent dewaxed oil, solvent-deasphalted oils, shale oil, coal tar.Iron therein can be with organism, exist as the form of iron naphthenate, ferrous porphyrin and derivative thereof, also can be with inorganics, exist as the form of the inorganic salt of iron, the compound of these iron can be dissolved in the oil, also can be mixed in the oil with the form of micro-solid particulate matter.

According to method provided by the invention, described contact temperature is 150-450 ℃, is preferably 180-400 ℃, and the hydrogen dividing potential drop is the 0.1-20 MPa, is preferably the 0.1-15 MPa, and hydrogen to oil volume ratio is at least 50, is preferably 100-1500, and weight hourly space velocity is 1-30 hour ^-1, be preferably 5-25 hour ^-1

The present invention adopts in the presence of hydrogen, will contain the stock oil and the mode that inert fiber shape material contacts of iron, reaches the purpose that fully removes iron in the stock oil, and the existence of hydrogen has promoted the fracture of carbon-sulfide linkage, has promoted the formation reaction of iron sulphide effectively.Therefore, compare, under same or lower temperature, can obtain higher deferrization rate with the non-hydrogen mode.

For example, adopting method provided by the invention, is that 12 MPas, hydrogen to oil volume ratio are 200 in the hydrogen dividing potential drop, and weight hourly space velocity is 10 hours ^-1And temperature is respectively under the condition of 230 ℃ and 200 ℃, stock oil to iron level 8.7 μ g/g carries out deferrization, the deferrization rate reaches 95.4 heavy % and 93.1 heavy % respectively, and adopt the method for non-hydrogen (is US4,933,071 described methods), 230 ℃ of temperature, under the identical condition of other conditions, the deferrization rate has only 44.8 heavy %.

Adopt method provided by the invention, in deferrization, can remove the part acidic cpd simultaneously, it is refining to make stock oil obtain part.For example under these conditions,, can remove the acid of 32.1-39.3% when adopting method provided by the invention simultaneously, adopt the method for non-hydrogen then can not remove acid in the stock oil same stock oil deferrization.

In addition,, avoided local too much sedimental generation, helped long-term operation because hydrogen to the dissemination of logistics, adopts method provided by the invention can also improve the distribution of liquid stream in bed.

Following example will the present invention will be further described.

Example 1-5

Remove iron in the stock oil by method provided by the invention.

At an internal diameter is 8 millimeters, and external diameter is that the 12 gram mean diameters of packing in 22 millimeters the reactor are 17 microns glass fibre, and loading height is 182 millimeters.The volume packing density of glass fibre (the shared volume of glass fibre accounts for the percentage ratio of cumulative volume) is 6%, and downflow system feeds 1 shown in the table 1 ^#Stock oil, 200 ℃ of temperature of reaction, 230 ℃, 270 ℃ and 350 ℃, hydrogen dividing potential drop 0.5 MPa and 12.0 MPas, weight hourly space velocity 10 hours ^-1With 20 hours ^-1, reacting under hydrogen to oil volume ratio 200 and 1000 the condition, table 2 has provided reaction conditions and result.

Comparative Examples 1

Press US4,933,071 disclosed methods remove the iron in the stock oil.

Method by example 4 is carried out deferrization to same stock oil, and different does not just feed hydrogen, and reaction result is listed in the table 2.

Table 1

The stock oil numbering	1 #	2 #
			The stock oil title	The carat horse is according to the mixing oil of No. 19 compressor oils of viscous crude and No. 45 transformer oil	The normal four line distillates of viscous crude
Density (20 ℃), g/cm 3	0.8729	0.9150
			Iron level, μ g/g	8.7	24.0
Acid number, mgKOH/g	0.28	9.20
			Sulphur content, μ g/g	400	500

Table 2

Example number	1	2	3	4	5	Comparative Examples 1
							Temperature of reaction, ℃	270	350	200	230	350	230
Hydrogen dividing potential drop MPa	0.5	0.5	12.0	12.0	12.0	12.0
							Hydrogen to oil volume ratio	200	200	200	200	1000	200
Liquid hourly space velocity, hour -1	10	10	10	10	20	10
							Generate oily iron level, μ g/g	0.6	0.3	0.6	0.4	0.4	4.8
The deferrization rate, heavy %	93.1	96.6	93.1	95.4	95.4	44.8
							Generate the oleic acid value, mgKOH/g	0.23	0.21	0.21	0.19	0.17	0.28
Acid removal rate, %	17.9	25.0	25.0	32.1	39.3	0

Example 6

Remove iron in the stock oil by method provided by the invention.

Remove iron in the stock oil according to the method for example 1, different is, and raw materials used oil is shown in the table 12 ^#Stock oil, the volume packing density of glass fibre is 8%, temperature of reaction is 390 ℃, the hydrogen dividing potential drop is 2.5 MPas, and reaction result is as follows: the iron level that generates in the oil is 0.8 μ g/g, and the deferrization rate is 96.7 heavy %, giving birth to olefiant acid number is 7.2mgKOH/g, and acid removal rate is 21.7%.

Claims (8)

1. a method that removes the iron in the petroleum fractions comprises a kind of iron content petroleum fractions is contacted with a kind of inert fiber shape material bed, it is characterized in that, described contact is to carry out under nitrogen atmosphere, the contact temperature is 150-450 ℃, the hydrogen dividing potential drop is the 0.1-20 MPa, hydrogen to oil volume ratio is at least 50, and weight hourly space velocity is 1-30 hour ^-1

2. method according to claim 1 is characterized in that, described inert fiber material is selected from one or more in glass fibre, charcoal fiber, rock wool, the silica wool.

3. method according to claim 1 and 2 is characterized in that, the mean diameter of described inert fiber material is not more than 50 microns.

4. method according to claim 3 is characterized in that, the mean diameter of described inert fiber material is not more than 20 microns.

5. method according to claim 1 is characterized in that, the volume packing density of described inert fiber bed is 2-15%.

6. method according to claim 5 is characterized in that, the volume packing density of described inert fiber bed is 5-10%.

7. method according to claim 1 is characterized in that, described contact temperature is 180-400 ℃, and the hydrogen dividing potential drop is the 0.1-15 MPa, hydrogen to oil volume ratio 100-1500, and weight hourly space velocity is 5-25 hour ^-1

8. method according to claim 1 is characterized in that, described iron content petroleum fractions is selected from crude oil, various distillates, solvent-refined oil, solvent dewaxed oil, solvent-deasphalted oils, shale oil, coal tar.