Method for metal removing from hydrocarbon stream

FIELD: treatment of hydrocarbon stream with adsorbent to remove metal component.

SUBSTANCE: hydrocarbon stream is brought into a contact with adsorbent containing (wt %): aluminum oxide 50-97 % and earth-alkali oxides selected from calcium oxide and magnesium oxide 50-3 % in oxide weight ratio of 10;1-50:50. Adsorbent has BET specific surface at least 100 m2/g and apparent porosity of 60-80 %. Process is carried out at 250-3500C.

EFFECT: method for removing of metal components.

3 cl, 3 tbl, 6 ex

 

Background of invention

This invention relates to the treatment of hydrocarbon streams using adsorbents effectively removing metal components that are often present in such streams.

The flow of hydrocarbons at the outlet of the refinery often contain metallic impurities in the form of organic or inorganic compounds of metals or of metals. These metal impurities can create serious problems, such as deactivation of the catalyst, the degradation properties of the metals used in industrial equipment, environmental hazard and toxic pollution. To avoid these harmful consequences, or at least weaken them, it is highly desirable to remove these substances from hydrocarbon streams.

The invention

This invention is a method of removing metallic impurities from a stream, which is based on the interaction of the flow of hydrocarbons from the adsorbent consisting of aluminum oxide in an amount of from 50 to 96 weight% and oxides of alkaline earth metals in an amount of from 50 to 4 wt.%, selected from the oxides of calcium and magnesium in a ratio of from 90:10 to 50:50, with a BET surface of at least 100 m2/, the Flow of hydrocarbons in contact with the adsorbent at a temperature between 20° s and 50° With and preferably between 250° 350° C.

Metals that can be removed from the flow of production oil with this invention include lead, aluminum, silicon, iron, chromium, zinc, magnesium, Nickel, sodium, calcium, vanadium, mercury, phosphorus and magnesium. As a rule, the flow of hydrocarbons contains hydrocarbons with five or more carbon atoms.

The term “adsorbent”as used in this invention means the ceramic materials of the composition in the form of tablets, balls, rods, or other form with a sufficient porosity (which affects the size of the surface) for physical capture metal impurities in the pores of the adsorbent, adsorption on the pore surface or, more often, for the chemical reaction of the impurities with the adsorbent substances with education components, which are not further transported by the stream.

Component ratio calculated from weights taken original components with the stoichiometric amendment to the oxides remaining after ignition of the inventive adsorbent. This operation allows one to obtain exact values, as can be seen from the examples that follow.

BoehmiteCaso3MgCO3Al2O3CaOMgO
908.21.892.26.61.2
6036465.931.13.0
963.60.497.12.60.3
962.02.0971.61.4

The first three were made with dolomite limestone and the fourth part is a simple dolomite. You can see that during the transition from the previous to the final calcined product relative change slightly.

The adsorbent may have a particular shape depending on the destination. For example, take the form of short rods or pellets, hollow cylinders, rings, pads, etc. are Particularly common form described in the patent USP 5,394,423. The adsorbent may also be applied in the form of monoliths with multiple holes, stacked layers. However, such solid adsorbents are often less preferred for the purposes stated in this invention.

It is believed that the most likely mechanism of metal removal from a stream of hydrocarbons involves the reaction of metal with the adsorbent. Adsorption of metal on the surface of the adsorbent is accelerated if and IU is all, and the polar adsorbent and placed in a nonpolar liquid (stream of hydrocarbons). This process is accelerated by heat. The activity of the adsorbent can be recovered by removing chemically held impurities using backwashing layer containing the deactivated adsorbent, hot (for example, at a temperature of 150° (C) water vapor. A fairly complete removal of impurities is achieved by steaming for 8 hours As noted above, before reactivation is desirable to remove heavy hydrocarbon residues from the pores of the adsorbent using a hydrocarbon solvent, such as toluene or other solvent enriched in aromatic hydrocarbons, type XYSOL™ (supplied by the company Trysol Canada Ltd. Of Calgary, Canada), preheated to a temperature of ~300° C.

Found that washing with hot methanol (for example, at a temperature of ~150° (C) between treatments solvent and water vapor helps to remove residual oils and facilitates the penetration of steam into the pores. The same effect is achieved by adding a certain amount of methanol to water vapor. Methanol is particularly effective, however, believe that it can be replaced by any low molecular weight alcohol, such as ethanol, n-propyl or isopropyl alcohol. The adsorbent can be prepared according to the method, including

a) education is Finance aqueous suspension, containing 50-97 wt.% hydrated alumina, such as boehmite, with the addition of from 50 to 3 wt.% a mixture of carbonates of calcium and magnesium with a relative ratio of carbonates of calcium and magnesium from 10:1 to 50:50, and the weight of boehmite and mixtures of carbonates given in the calculation of the weight of the solid components of the suspension;

b) peptization suspension by adding an acid;

c) extruding patinirovannoy suspension with the formation of the particles of the adsorbent desired shape and

d) drying to remove water and calcination at temperatures from 650 to 850° C.

Hydrated aluminum oxide can be, for example, from any commercial boehmite, which is credited with formula lOO or more precisely Al2O3·H2O.

A mixture of carbonates of calcium and magnesium usually consists of dolomite powder, or preferably dolomitic limestone, which is a mixture of dolomite (in which calcium and magnesium are contained in approximately equal atomic amounts) and calcite dominated by calcite, and also contains a few percent of impurities such as silica and iron. During annealing the mixture is decomposed to the corresponding oxides. Therefore, the claimed products, in principle, can be prepared by adding oxides or hydroxides in suspension of boehmite. However, this would require more acid to which epitacio suspension and therefore less preferable.

For dispersion of carbonates in the ash of boehmite preferably in the form of a powder with an average particle size of about 50 microns or less. These requirements satisfies sales dolomitic limestone from National Lime and Stone Company under the trademark Bucyrus Microfine (99% of the powder passes through a sieve of 325 mesh). This product contains carbonates of calcium and magnesium in a weight ratio of about 6:1.

Acid, which is added for peptization of the suspension, which is a variance component containing calcium/magnesium in the ash of the boehmite may be selected from acids, traditionally used for peptization of such sols. Since the annealing leads to the decomposition of the acid, it is preferable to apply mineral acids such as nitric, hydrochloric or sulfuric, and strong organic acids, for example acetic or better ant. Reptitiously Sol must be stable, so that when forming, for example, by extrusion, it was possible to obtain samples that retains shape while drying and calcination. It is enough to add such an amount of acid to lower the pH to 5 or below.

Drying of samples is preferably carried out in such conditions, to avoid damage during the removal of water. This is achieved at a low temperature of about 100° With (although in most cases the temperature is slightly above 50° C) in t is the significance of a prolonged period of time up to two days, although usually for drying enough 10-24 hours

For the formation of oxides of calcium and magnesium from the corresponding carbonates, removal of bound water and the transformation of boehmite to gamma alumina or other allomorphy or amorphous modifications, calcining the dry samples should be long. However, it is preferable to choose such conditions of calcination, in order to avoid the formation of alpha-alumina or sintering, which leads to a reduction of porosity and the conversion of aluminum oxide in a less active form. Therefore, it is preferable to conduct the calcination at the temperature of maximum 500-800° and prior to the termination of weight loss. Typically, heating at a temperature of annealing for a time from 30 minutes to 5 hours is sufficient to decompose all of carbonates and delete all associated water.

The value of the surface of the calcined product is not less than 100 m2/g, e.g., above 250 m2/g and preferably from 200 to 250 m2/year

Description of the preferred variants of the invention

The following are examples illustrating how the inventive adsorbent effective in removing contaminants from hydrocarbon streams.

In further examples, the identification of individual elements was carried out using tr Tech System Ltd. of Calgary, Canada.

In examples 1-4 was used, the flow angle is of hydrogens, contains 48 metal impurities in varying amounts identified in density in degrees American petroleum Institute. Stream is pumped through a heated column of stainless steel with a length of 25 cm and a diameter of 1.27 cm, filled with 8 g of adsorbent. In all cases, the adsorbent had the following properties. The magnitude of the surface by the BET was $ 219 m2/g, apparent porosity 78.5%, adsorption of water 103.4%, the apparent density of 3.54 g/cm3and the density of 0.76 g/cm3.

Analysis of the adsorbent showed that it contains 92.2 wt.% aluminum oxide, 6.6 wt.% of calcium oxide and 1.2 wt.% magnesium oxide.

Example 1

In the first experiment, a stream of hydrocarbons containing 24 ppm of iron, 2 ppm of zinc, and 2 ppm of lead, is passed through the above-described adsorbent with a speed of 3.1 ml/min Initial temperature of the support at the level 273.9° C, after 60 h to raise 301.7° and after 120 h again raised to 315.6° C. the Number of remote metals after a specified number of hours, expressed as a percentage of ppm element in the stream, are shown in table 1.

Table 1
TIME/HLEADIRONZINC
610087100
12 10085100
242481100
361488100
483895100
60*10098100
7210098100
84100100100
963396100
1083997100
120*38100100
13239100100
14439100100
1569699100
16210096100
1747891100
186100100100
1988393100
2009199100

*Shows temperature rise.

Example 2

After 200 HR column was washed with toluene and regenerates water vapor, as described above. This experience is held at 315.6° when soon the minute flow 3.1 ml/min The flow of hydrocarbons contained the same impurities and in the same amount as in example 1. The results are shown in table 2, where each column shows the number of deleted items in the percentage ppm present element.

Table 2
TIME/HLEADIRONZINC
6100100100
24100100100
36100100100
48100100100
60100100100
72100100100
84100100100
96100100100
108100100100
120100100100
132100100100
144100100100
156100100100
162100100100

P the emer 3

After the experience, which lasted 162 h as described in example 2, the flow of hydrocarbon is replaced with a stream containing these metal impurities: iron - 116 ppm; zinc - 2 ppm; lead - 3 ppm; aluminum - 223 ppm; magnesium - 49 ppm; sodium - 38 ppm; calcium - 57 ppm and manganese - 1 ppm

The experience continued for 24 h under the conditions described in example 2. Sampling after 12 and 24 h showed that during this time each impurity was removed by 100%.

Example 4

In this example, we studied the effect of temperature on the removal of various elements. Experimental conditions were the same as in the above examples, but with the new loading of the adsorbent and the flow of hydrocarbons containing: mercury - 6 ppm; copper - 2.6 ppm; iron - 8.9 ppm; zinc - 0.1 ppm and the phosphorus - 8.2 ppm Stream was passed with a speed of 3.1 ml/min for 6 h at temperatures varying as shown in table 3.

Table 3
TIME/H1356
TEMP (°)110210280280
Mercury50%66%77%85%
Copper81%96%100%100%
Iron0%30%/td> 100%100%
Zinc100%100%100%100%
Phosphorus100%100%100%100%

Example 5

In this example, the estimation of the adsorbent in the pilot unit using a flow of hydrocarbons destined for processing. The flux density in degrees American petroleum Institute was 45-50, the water content of 1-10% solids 1-3%. The bulk water and the precipitate was removed, and the stream was pumped through two Teploobmennik and the heater to raise the temperature to between 248.9° and 315.6° C. Then the hot air stream was passed through the layer containing approximately 1.87 m3(66 cubic feet) of the same adsorbent as in the previous examples. The volume of flow ranged from 25 to 38 per day. The pressure in the stream ranged from 517 kN/m2620 kN/m2(75 to 90 mm Hg), and 50-60% due to steam. The steam flow was separated and did not pass through the adsorbent. After passing the liquid stream through a bed of adsorbent was connected with a steam stream and sent to a distillation column. After processing all of 2,300 barrels of oil was obtained following purification (interest deleted metals): phosphorus - 98%; sodium - 72%; iron - 95%; aluminum - 97%; copper - 92%; qi is to - 99%; calcium - 94%; magnesium - 98%; silicon - 77%; lead - 49% and chrome - 89%.

The sample taken after treatment 1,900 barrels contain iron, calcium, sodium, magnesium, aluminum, silicon and phosphorus. After passing a flow of hydrocarbon through a bed of the adsorbent, the degree of removal of these elements were: calcium - 90%; sodium - 73%; magnesium - 98%; aluminum - 95%; iron - 92%; silicon - 15% and the phosphorus - 96%.

Example 6

In this example, the flow of hydrocarbons represented crude oil from Northern Alberta (Northern Alberta)containing zinc, Nickel, sodium, and vanadium. A sample of this material was placed in the autoclave with 10 g of the adsorbent used in the previous examples. The autoclave was heated to 300° when the nitrogen pressure 689 kN/m2(100 mm Hg). After 30 min the sample was analyzed and found that were removed 45% Nickel, 21% sodium, 76% of sodium and 24% vanadium.

The examples are not restrictive. Successful results have been obtained by the applicant for the testing of adsorbents with different values of the surface according to BET- 109, 112, 115, 199, 274 m2/year

1. Method of removing metals from a stream of hydrocarbons, which consists in contact flow of hydrocarbons from the adsorbent containing from 50 to 97 weight. % of aluminum oxide and 50 to 3 weight. % alkaline earth oxides selected from oxides of calcium and magnesium, with the weight ratio of the oxides from 10:1 to 50:50, and adsorbed what is the value of the surface by BET at least 100 m 2/year

2. The method according to claim 1, characterized in that the adsorbent has an apparent porosity of from 60 to 80%.

3. The method according to claim 1, characterized in that it is carried out at a temperature from 250 to 350°C.



 

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FIELD: treatment of hydrocarbon stream with adsorbent to remove metal component.

SUBSTANCE: hydrocarbon stream is brought into a contact with adsorbent containing (wt %): aluminum oxide 50-97 % and earth-alkali oxides selected from calcium oxide and magnesium oxide 50-3 % in oxide weight ratio of 10;1-50:50. Adsorbent has BET specific surface at least 100 m2/g and apparent porosity of 60-80 %. Process is carried out at 250-3500C.

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6 tbl, 9 ex

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