CN1045305C - Saturation hydrogenating process for removing olefines from reforming produced oil - Google Patents
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Abstract
The present invention relates to a selective hydrogenation technology used for removing alkene from reformation generated oil. In a magnetic stabilization bed reactor, the liquid reformation generated oil and hydrogen are in contact with ferromagnetic hydrogenation catalysts. The reaction has the conditions that the reaction temperature is from 50 to 220 DEG C, the reaction pressure is 0.1 to 3MPa, the reaction air speed is from 2 to 40 h<-1>, and the ratio of hydrogen to oil is from 40 to 150. Compared with the prior art, the technology has the advantages of low temperature, low pressure, high air speed, high alkene conversion rate, good selectivity, no loss of arene, no environment pollution, no interference for the water and chlorine balance of reforming catalysts, etc.
Description
The present invention relates to hydrofining technology for reformed oil, specifically about a kind of magnetic stablizing bed saturation hydrogenating process for removing olefines from reforming produced oil.
Catalytic reforming is the important process process from oil production aromatic hydrocarbons and high octane gasoline component, owing to have hydrocracking reaction in the reforming reaction process, therefore, contain small amounts of olefins in the reformed oil, for being the catalytic reforming process of purpose to produce aromatic hydrocarbons, the existence of alkene will influence the colourity and the stability of product, thereby must be removed.
At present, remove that the technology of small amounts of olefins mainly contains two kinds in the reformed oil, promptly clay-filtered technology and back end hydrogenation technology.Clay-filtered technology is the alkene that utilizes in the carclazyte absorption aromatic hydrocarbon product, to reach the purpose of removing alkene, the carclazyte activity is lower, life cycle short, easily cause shortcomings such as environmental pollution and air speed are lower owing to exist, thereby this technology has the trend that is replaced by back end hydrogenation technology.Traditional back end hydrogenation technology on flow process is, the generation oil of last reforming reactor outlet and hydrogen are through an interchanger, fluid temperature (F.T.) is reduced to about 330 ℃, enter the back end hydrogenation reactor that hydrogenation catalyst is housed then, make the hydrogenation of olefins that generates in the oil, though it is simple that back end hydrogenation technology has flow process, energy consumption is low, there is not advantages such as " three wastes ", but, along with progressively applying of two (many) metal reforming catalysts in recent years, the raising of resurfacing operation severity, this technology can influence the water chloride balance control of reforming catalyst, increases the pressure drop of recycle hydrogen system, and is improper if operational condition and control have slightly, also can make the part aromatic hydrogenation in the reformed oil saturated, simultaneously, temperature of reaction also is difficult to control in the back end hydrogenation technology, catalyzer regeneration separately during shut-down.Therefore, develop a kind of novel saturation hydrogenating process for removing olefines from reforming produced oil,, become the problem that currency must be studied to eliminate the shortcoming that exists in the existing technology.
The sixties in this century, Filippov has proposed a kind of novel bed form, be magnetically fluidized bed (Magnetically Fluidized Bed), sixties end, Tuthill (US 3440731) has proposed the notion of magnetic stablizing bed (Magretically Stabilized Bed) on this basis again, it forms under axial, time-independent even externally-applied magnetic field effect, has only the stable bed of faint motion.The result of study of the stable bed that crashes shows, it has some characteristic of fixed bed and fluidized-bed concurrently, both can as fluidized-bed, use the small-particle solid and be unlikely to cause too high pressure to fall loss with solid particulate, can not have tangible solid flow again as fixed bed, back-mixing has between phase and phase been controlled in the effect of externally-applied magnetic field effectively.Uniformly voidage makes bed inside not be prone to channel again, simultaneously, magnetic stablizing bed can also bubble crushing, improve mass transfer between phase and phase, and have advantages such as operation field width, stable operation, transmission effect are good.
In recent years, research to magnetically fluidized bed and magnetic stablizing bed character and application is very active, Siegell (powder Technology 64,1～181,1991) summarized gas-solid, liquid-solid magnetically fluidized bed and magnetic stablizing bed character and application, wherein, people such as Znunchev, people such as Sonolikar use it for process (the Powder Technology 64 of synthetic ammonia, 6,1991), Hare (powder Technology 64,159,1991), Liu (AICHE Annual Meeting, LosAngeles, CA, Nov., 1982), Cohen (powder Technokgy 64,147,1991) etc. the people is used for the filtration procedure of dedusting and waste gas with magnetically fluidized bed and magnetic stablizing bed as strainer.
People such as Rosensweig (US4136016) are with the magnetic stablizing bed hydrocarbon conversion process that is used for, as unifining process, catforming process etc., but their used bed is that gas-solid is magnetic stablizing bed, being its reaction raw materials is the hydro carbons through having gasified, perhaps hydrogen and gasoline through having gasified, and in unifining process, its temperature of reaction is (500～800 °F) up to 260～427 ℃.The solid magnetic stablizing bed application aspect hydrofining of (as being lower than 220 ℃) gas-liquid does not appear in the newspapers or disclosure under the lesser temps.
Solid magnetic stablizing bed about gas-liquid, then only find the application of people (chemical industry journal 1 (1), 20,1988) aspect the immobilized cell processing such as Hu Zongding.
Therefore, magnetic stablizing bed superior performance has shown it in industrial application prospect, but solid magnetic stablizing bed to be applied to hydrorefined process still be a blank with gas-liquid under the lesser temps, fills up this blank, not only has the value of industrial application.And adapted to the trend that unifining process develops to the low temperature direction.
About the saturated hydrogenation catalyzer of alkene, summary gets up to have following several, that is:
(1) Mo-Co-Al that uses of traditional reformed oil back end hydrogenation technology
2O
3Catalyzer, its use temperature are generally about 330 ℃.
(2) Raney nickel (Raney Ni) catalyzer is characterized in having higher activity, can catalysis low temperature (being lower than 220 ℃) the saturated hydrogenation reaction of alkene down.
(3) amorphous alloy catalyst of nickeliferous or cobalt or iron is comprising the big surface amorphous alloy catalyst (CN95116430.9) of olefine saturation hydrogenation activity apparently higher than Raney nickel.
Above-mentioned Raney nickel and amorphous alloy catalyst, there is no the report that is useful on olefine saturation hydrogenation in the reformed oil, do not see yet and be useful on magnetic stablizing bed report, yet these two kinds of catalyzer are not because granularity all less (20 orders are following) is suitable for fixed-bed reactor, and when being used for fluidized-bed reactor, granules of catalyst is easy to be taken out of by fluid, and therefore, the practical application that has the catalyzer of hydrogenation activity under the low temperature also becomes the problem that needs solution when previous.
Purpose of the present invention promptly provides the saturation hydrogenating process for removing olefines from reforming produced oil that a kind of temperature of reaction is low, air speed is big, olefin conversion is high and hydrogenation selectivity is good.
Saturation hydrogenating process for removing olefines from reforming produced oil provided by the invention can be realized by technical process as shown in Figure 1.Be that reformed oil is exported by volume pump (A), through giving hot device (B) and tensimeter (C), enter the magnetically stabilized bed reactor of controlling by externally-applied magnetic field (E) (F) with hydrogen by tensimeter (D), and with reactor (F) in have hydrogenation activity under the low temperature beds contact, it is solid magnetic stablizing bed to form gas-liquid, under given reaction process condition, alkene is carried out selective hydrogenation, reaction product and unreacted hydrogen enter separator (H after water cooler (G) cooling, I), unreacted hydrogen is discharged and is recycled through surge tank (J) by the top of separator (I), and liquid product is collected by the bottom of separator (I).
In the technology provided by the invention, described magnetically stabilized bed reactor is made up of reaction tubes and externally-applied magnetic field, externally-applied magnetic field is a uniform steady magnetic field vertically, this magnetic field is by direct supply and a series of and co-axial Helmholtz of reaction tubes (Helmhotz) coil or evenly closely provide around solenoid coil, and reaction tubes is made by the good stainless steel of magnetic permeability.Should be noted that, the size of externally-applied magnetic field and reactor big or small closely related, when reactor is big, the intensity of the externally-applied magnetic field that needs should be stronger, it is used helmholtz coil/evenly close bigger around solenoidal power, or coil/solenoidal number of turn is more, or used coil/solenoidal number is more, and vice versa.
In the technology provided by the invention, described magnetic stablizing bed be meant gas-liquid-solid three-phase and deposit magnetic stablizing bed, its operational stage, be that the bed form is (as Fig. 3, Fig. 4, shown in Figure 5) and corresponding with it in bed, form bubble form (as Fig. 6, Fig. 7, shown in Figure 8) show three kinds of states with the change of magneticstrength, when magneticstrength hour, magnetic field is less to particulate magnetization degree, intergranular interaction force is little, particle all is present in the single particle state does free movement in the bed, bed shows as shot state (as shown in Figure 3) at this moment, bed voidage is bigger, the bed back-mixing is more serious, and the bubble that forms in bed is for playing shape bubble (as shown in Figure 6).When magneticstrength is brought up to certain value, particle in the bed is because the effect of magnetic force, dimerization, trimerization and even poly take place between the particle, the chain type state that formation is lined up along the magnetic line of force direction forms chain type bed (as shown in Figure 4), and this moment, bed voidage was also bigger, the bed operation is highly stable, the bed surface particle has obvious motion, and the bed endoparticle has only faint motion, and the bubble that forms in bed is a uniform roundlet bubble (as shown in Figure 7).After magneticstrength continues to bring up to a certain value; because magneto motive enhancing between the particle; all particles bunch up in the bed; form the poly-state (as shown in Figure 5) of magnetic; at this moment; voidage is bigger, if liquid speed improves, all bed particles can be a whole upwards drift; after exceeding magnetic field range; be scattered in the pipeline, form the loose granule skeleton, under the poly-state of magnetic; permitted great passage in the bed body; gas, liquid can form channel from local major path by bed, and at this moment, the bubble that forms in bed is flat bubble (as shown in Figure 8).In above-mentioned three kinds of magnetic stablizing bed operational stage, ideal state is the operational stage (as shown in Figure 2) with chain type bed and even roundlet bubble.
In the technology provided by the invention, described magnetic stablizing bed operational stage is also relevant with pressure with the temperature of reaction, be that temperature of reaction and pressure must be able to keep reformed oil to be in liquid state all the time, or major part is in liquid state, after temperature is brought up to a certain value or pressure and is reduced to a certain value, reformed oil will all gasify or most of gasification, and magnetic stablizing bed operational stage will be with the magnetic stablizing bed appearance of gas-solid.This has just exceeded the scope that the present invention relates to.
In the technology provided by the invention, employed catalyzer is to have hydrogenation activity under the low temperature (being lower than 220 ℃), and catalyzer with magnetic, the magnetic of catalyzer can be provided by the magnetic that catalyst themselves had, also can be by mixing, various complex methods such as adhesion, embedding are (as U4687878,4541924,4541925, the method that EP149343 provides) it is compound to have the material (as be selected from nickel, cobalt, iron or its oxide compound one or more) and a non-magnetic catalyst activity component of magnetic, be prepared into matrix material, make catalyzer have magnetic.
In above-mentioned catalyzer, preferred catalyzer is to have ferromagnetic hydrogenation catalyst, as contains one or more the hydrogenation catalyst that is selected from nickel, cobalt, iron or their oxide compound.
Have in the ferromagnetic hydrogenation catalyst above-mentioned, more preferred catalyzer is that (its preparation method is referring to " Preparation of Catalyst handbook for Raney nickel catalyst, Chemical Industry Press, P608～609,1982) and contain nickel, cobalt, the amorphous alloy catalyst of iron or their mixtures, as J.Catal.99,375, the Ni-P-La and the Ni-P amorphous alloy catalyst of 1986 reports, petroleum journal 7 (2), 86～89,1991 and Journal of Molecular Catalysis 5 (4), the Ni-Y-P amorphous alloy catalyst of 272～275,1991 reports and the Ni-P amorphous alloy that discloses as the JP86119606 that catalyzer uses, the Ni-Zr amorphous alloy that EP173088 discloses etc.
In the above-mentioned amorphous alloy catalyst, one of highly preferred catalyzer is nickel or cobalt or the iron that consists of 86～92.5 heavy %, the rare earth of 0～3 heavy % and the big surface amorphous alloy catalyst of Ni/Co/Fe-RE-P (its preparation method is referring to CN1073726A) of surplus phosphorus.
In the above-mentioned amorphous alloy catalyst, two of highly preferred catalyzer is the nickel that consists of 40～91 heavy %, the high-ferromagnetic non-crystalline alloy catalyst of 2～40 heavy % iron and surplus phosphorus.(referring to application " a kind of high-ferromagnetic non-crystalline alloy catalyst " on the same day) its preparation method is as follows:
(1) preparation Ni-P mother alloy will add in the quantitative phosphorus after the quantitative nickel fusion, and the two is alloying voluntarily.
(2) quantitative iron and aluminium are given in adding in above-mentioned mother alloy, make the weight of aluminium account for 50% of gross weight, refine in vacuum smelting furnace then, get the mother alloy that Ni-Fe-P and Al respectively account for 50 heavy %, are designated as (Ni-Fe-P)
50Al
50
(3) with vacuum quench (open clear 61-212332 referring to the spy and reach wherein Fig. 2) fast quenching (Ni-Fe-P)
50Al
50Mother alloy, fast quenching condition are copper roller linear velocity 20～40 meter per seconds, spraying pressure 0.05～0.1MPa, 1400～1500 ℃ of injection temperatures.
(4) with fast quenching gained (Ni-Fe-P)
50Al
50Place 10～25 heavy % sodium hydroxide solutions, placed 0～2 hour for 0～50 ℃, be warming up to 50～110 ℃, constant temperature is handled and was promptly got the Ni-Fe-P high-ferromagnetic non-crystalline alloy catalyst in 1～5 hour, and wherein sodium hydroxide concentration is to be advisable to aluminium excessive 20～30 heavy %.
For technology provided by the invention, the raising of temperature of reaction can improve the conversion of olefines rate, under the identical situation of other conditions, the setting of temperature of reaction should change with the difference of stock oil bromine valency again, temperature of reaction was answered corresponding raising when the bromine valency was high, vice versa, and temperature of reaction can be 50～220 ℃, best 70～200 ℃.The raising of reaction pressure can make molecular balance move to the direction of conversion of olefines, thereby, also can improve the conversion of olefines rate, but after reaction pressure is higher than 1MPa, it is not too obvious that reaction pressure continues to improve the effect that olefin conversion is improved, in order to cut down the consumption of energy, the scope of reaction pressure is decided to be 0.1～3.0MPa, best 1～2MPa.The raising of reaction velocity (referring to reformed oil liquid volume air speed) can reduce the conversion of olefines rate, and reaction velocity can be 2～40h
-1, best 4～30h
-1The increase of hydrogen-oil ratio (volume ratio of hydrogen and liquid reformed oil) helps molecular balance and moves to the direction of conversion of olefines, but energy consumption is considered in this effect and not obvious simultaneously, thereby with fixed lower of hydrogen-oil ratio, be that hydrogen-oil ratio is 30～150, best 50～100.
Technology provided by the invention can be connected in after first oil-gas separator with the supporting use of catalytic reforming the time, also can be connected in after the depentanizer, and is discrete and put with reforming system.
Technology provided by the invention has following advantage:
(1) temperature of reaction is low, and temperature of reaction has only 50～220 ℃, therefore, on stream can be without process furnace, directly give heat and can reach requirement temperature of reaction by interchanger.
(2) olefin conversion height, selectivity is good, can not cause the loss of aromatic hydrocarbons, as uses Ni
87.4-La
0.4-P
122Big surface amorphous alloy is as catalyzer, at 170 ℃ of temperature of reaction, reaction pressure 1MPa, reaction velocity 4h
-1Under the reaction conditions of hydrogen-oil ratio 100, (the bromine valency is represented the content of alkene here to the bromine valency, its measuring method is referring to " petrochemical complex analytical procedure " RIPP test method, Science Press, P172～175,1990) carry out hydrogenation for the stock oil of 3.9g/100g, the bromine valency of product drops to 0.2g/100g, and the content of aromatic hydrocarbons becomes 63.03 heavy % from 62.95 heavy %.And adopt traditional back end hydrogenation technology Mo-Co-Al
2O
3As catalyzer, at 330 ℃ of temperature of reaction, reaction pressure 1.61MPa, air speed 4.5h
-1Reaction conditions under, the bromine valency is that the bromine valency of the stock oil hydrogenation after product of 0.7g/100g also only drops to 0.2g/100g.
(3) air speed is big, and the device processing power is big, as uses Ni
87.4-La
0.4-P
122Big surface amorphous alloy is as catalyzer, 170 ℃ of temperature of reaction, air speed 12h
-1The time, can make the bromine valency of reformed oil drop to 0.34g/100g, and adopt traditional back end hydrogenation technology, Mo-Co-Al from 3.7g/100g
2O
3As catalyzer, in temperature of reaction up to 330 ℃, air speed 4.5h
-1, only make the bromine valency of reformed oil drop to 0.2g/100g from 0.7g/100g.When using the Ni-Fe-P high-ferromagnetic non-crystalline alloy as catalyzer, temperature of reaction is further reduced, air speed further increases, and as 100 ℃ of temperature of reaction, air speed is up to 30h
-1Under use Ni
78.4-Fe
2-P
19.6Amorphous alloy catalyst makes the bromine valency of reformed oil drop to 0.42g/100g from 3.7g/100g, and the bromine valency of product still can satisfy the processing requirement that is lower than 0.5g/100g.
In addition, technology provided by the invention have also that flow process is simple, stable operation, be convenient to that control, bed mass transfer are effective, granules of catalyst little easy to loading and unloading, hydrogen-oil ratio is little, energy consumption low and do not influence advantage such as reforming catalyst water-chlorine balance.
Fig. 1 is a saturation hydrogenating process for removing olefines from reforming produced oil schematic flow sheet provided by the invention;
Fig. 2 is the magnetic stablizing bed operational stage synoptic diagram of ideal;
Fig. 3 is magnetic stablizing bed shot view;
Fig. 4 is magnetic stablizing bed chain type view;
Fig. 5 is the magnetic stablizing bed poly-view of magnetic;
Fig. 6 is the bullet shape bubble synoptic diagram that forms in magnetic stablizing bed;
Fig. 7 is the roundlet bubble synoptic diagram that forms in magnetic stablizing bed;
Fig. 8 is the flat bubble synoptic diagram that forms in magnetic stablizing bed.
The following examples will be further specified the present invention, but the present invention is not subjected to the restriction of following embodiment.
Magnetically stabilized bed reactor used among the embodiment is 55 millimeters by the reaction tubes of 14 millimeters of internal diameters with at four internal diameters that react tube wall outer reaction tubes axial arranging, external diameter is 165 millimeters, highly be 35 millimeters, the number of turn is that the helmholtz coil of 370 circles is formed, and the distance between the adjacent windings is 27.5 millimeters.The content of aromatic hydrocarbons is the 3700 type chromatographic instrument analyses of producing with Beijing Analytical Instrument Factory in raw material and the product, and chromatographic column is the FFAP chromatographic column.
Example 1～9
Technology provided by the invention can be carried out the olefine saturation hydrogenation reaction of reformed oil under different externally-applied magnetic field intensity.
With 10 milliliter of 60～90 purpose Ni
87.4-La
0.4-P
122Big surface amorphous alloy catalyst (its preparation method is referring to CN1073726A) and 5 milliliter of 180～200 purpose iron powder mix, in the magnetically stabilized bed reactor of packing into then, at 70 ℃ of temperature of reaction, reaction pressure 0.5MPa, air speed 12h
-1, under the processing condition of hydrogen-oil ratio 130, be that the reformed oil of 1.68g/100g carries out hydrogenation to the bromine valency, operational stage and reaction result under the different magnetic field intensity are shown in Table 1.
The presentation of results of table 1 in technology provided by the invention, with the raising of magneticstrength, magnetic stablizing bedly shows three kinds of operational stage successively, i.e. shot state, and the bubble that forms in bed is for playing the shape bubble; Chain type state, the bubble that forms in bed are the roundlet bubble; Magnetic gathers state, and the bubble that forms in bed is flat bubble.Under three kinds of operational stage, when temperature only is 70 ℃, all can make the olefine saturation hydrogenation in the reformed oil.The bromine valency that makes reformed oil drops to below the 0.5g/100g from 1.68g/100g and satisfies the requirement of technology, in three kinds of operational stage, especially with chain type state the best, when promptly magneticstrength is 133.8～230.5Oe, reaction effect is best, and the bromine valency of product can be reduced to 0.24～0.28g/100g.
Table 1
| Example number | Magneticstrength Oe | The bed form | Bubble form | Product bromine valency g/100g |
| 1 2 3 | 33.5 66.9 100.4 | The shot state | Play the shape bubble | 0.46 0.48 0.47 |
| 4 5 6 | 133.8 200.7 230.5 | The chain type state | The roundlet bubble | 0.24 0.27 0.28 |
| 7 8 9 | 267.7 401.4 835.2 | Magnetic gathers state | Flat bubble | 0.41 0.38 0.39 |
Example 10～16
Technology provided by the invention has the low characteristics of temperature of reaction.
Catalyzer is with example 1, and stock oil is bromine valency 3.7g/100g, the reformed oil of aromaticity content 67.24 heavy %, and the processing condition of reaction are pressure 1MPa, air speed 12h
-1, hydrogen-oil ratio 100, magneticstrength 133.8Oe.Reaction result under the differing temps is shown in Table 2.
The presentation of results of table 2, technology provided by the invention is lower than below 220 ℃ and can carries out in temperature of reaction, when being 170 ℃ as temperature of reaction, can make the bromine valency of reformed oil reduce to 0.34g/100g by 3.7g/100g, and can not make aromatic hydrogenation saturated and cause the loss of aromatic hydrocarbons, this adds bright technology provided by the invention and has the good advantage of selectivity, the result of table 2 illustrates that also the raising of temperature of reaction can improve the conversion of olefines rate, the result of associative list 1 can find out, in technology provided by the invention, temperature of reaction should change with the change of stock oil, when the bromine valency of stock oil is higher, should use higher temperature of reaction, and the bromine valency is when low, temperature of reaction can correspondingly reduce.
Table 2
| Example number | Temperature of reaction ℃ | Product bromine valency g/100g | The heavy % of aromaticity content |
| 10 11 12 13 14 15 16 | 40 70 100 120 150 170 200 | 1.8 1.2 0.79 0.74 0.53 0.34 0.10 | 67.38 67.57 67.85 67.43 67.44 67.32 67.35 |
Example 17～19
Technology provided by the invention can be carried out under different reaction pressures.
Catalyzer, reaction raw materials and reaction conditions be with example 15, just reaction pressure be respectively 0.5,1.0,1.5MPa, reaction result is shown in Table 3.
The presentation of results of table 3, technology provided by the invention can be carried out under different reaction pressures, pressure is to reacting favourable, be that the reaction pressure raising can improve the conversion of olefines rate, still, after reaction pressure is higher than 1MPa, it is also not obvious that reaction pressure improves the effect that olefin conversion is improved again, in order to cut down the consumption of energy, the present invention is decided to be 0.1～3.0MPa with the reaction pressure scope, best 1～2MPa.
Table 3
| Example number | Reaction pressure (MPa) | Product bromine valency g/100g | The heavy % of aromaticity content |
| 17 18 19 | 0.5 1.0 1.5 | 1.5 0.34 0.30 | 68.45 67.32 67.50 |
Example 20～23
Technology provided by the invention can be carried out under the differential responses air speed.
Catalyzer and reaction conditions are the air speed difference with example 15, and reaction raw materials is bromine valency 3.9g/100g, the reformed oil of aromaticity content 62.95 heavy %, and the reaction result under the different air speeds is listed in the table 4.
The presentation of results of table 4, technology provided by the invention can be carried out under different air speeds, and reaction velocity can be 2～20h
-1
Table 4
| Example number | Reaction velocity -1 | Product bromine valency g/100g | The heavy % of aromaticity content |
| 20 21 22 23 | 4 12 16 20 | 0.2 0.32 0.51 0.69 | 63.03 63.49 62.90 63.69 |
Example 24～27
Technology provided by the invention can be carried out under the different hydro oil ratio.
Catalyzer, reaction raw materials and reaction conditions are with example 21, and just hydrogen-oil ratio is respectively 50,70,100,130, and reaction result is listed in the table 5.
The presentation of results of table 5, technology provided by the invention, can under the different hydro oil ratio, carry out, the raising of hydrogen-oil ratio helps molecular balance and moves to the direction of conversion of olefines, but this raising and not obvious and too high hydrogen-oil ratio can increase energy consumption, therefore the present invention fixes on a lower level with hydrogen-oil ratio, and promptly hydrogen-oil ratio can be 30～150, and preferably 50～100.
Table 5
| Example number | Hydrogen-oil ratio | Product bromine valency g/100g | The heavy % of aromaticity content |
| 24 25 26 27 | 50 70 100 130 | 0.39 0.38 0.32 0.32 | 63.32 63.02 63.49 63.31 |
Comparative example 1
Adopt traditional back end hydrogenation technology, with Mo-Co-Al
2O
3During for catalyzer, reformed oil is carried out hydrogenation, its reaction conditions and the results are shown in Table 6 (selecting from " Chinese oil Refining Technologies ", Sinopec press, P176,1990).For contrasting conveniently, listed file names with the reaction conditions and the result of example 15 in the table 6.
The presentation of results of table 6, the temperature of reaction that technology provided by the invention adopted is significantly less than the temperature of reaction of prior art, and the rate of conversion of olefines simultaneously is much higher than prior art, and its reaction velocity also is much higher than prior art, in addition, also has lower reaction pressure.
Table 6
| Example number | Comparative example 1 | Example 15 |
| Technology category catalyst reaction temperatures ℃ reaction pressure MPa air speed h -1Reaction raw materials bromine valency g/100g product bromine valency g/100g | Back end hydrogenation technology Mo-Co-Al 2O 3 330 1.61 4.5 0.7 0.2 | Technology Ni-RE-P 170 1.0 12 3.7 0.34 provided by the invention |
Example 28
The Ni that is used for technology provided by the invention
78.4-Fe
2-P
19.6The high-ferromagnetic Preparation of catalysts.
1. 39.2g phosphorus is placed on compacting in the crucible, will pours in the crucible that phosphorus is housed after 9.8g nickel (technical pure) fusion, nickel and phosphorus is alloying voluntarily, gets the Ni-P mother alloy after the cooling.
2. add 1.0g iron (technical pure) and 50g aluminium (technical pure) in above-mentioned Ni-P mother alloy, place vacuum toggle stove then, treat to stop 10 minutes after its fusion again, vacuum tightness is 10 in this stove
-1～10
-2Torr, temperature are 1400 ℃, charge into argon gas to normal pressure then and make the Ni-Fe-P-Al mother alloy, are designated as (Ni-Fe-P)
50Al
50
3. with vacuum quench (open clear 61～212332 referring to the spy and reach wherein Fig. 2) preparation fast quenching (Ni-Fe-P)
50Al
50Mother alloy, fast quenching condition are copper roller linear velocity 30 meter per seconds, spraying pressure 0.08MPa, 1450 ℃ of injection temperatures.
4. remove fast quenching (Ni-Fe-P)
50Al
50In aluminium, with the fast quenching (Ni-Fe-P) that makes
50Al
50Place the sodium hydroxide solution of 481g, 20 heavy %, at room temperature placed 1 hour, be warming up to 80 ℃ and constant temperature then 2 hours, high-ferromagnetic Ni
78.4-Fe
2-P
19.6Amorphous alloy catalyst.
The Ni78.4 that consists of of above-mentioned Ni-Fe-P amorphous alloy catalyst weighs %, the heavy % of Fe2, the heavy % of P19.6, initial susceptibility 2.85 * 10
-2Emu/Oe.g.BET surface-area 98m
2/ g, active surface area 12.2m
2/ g.
The measuring method of initial susceptibility is as follows: take by weighing quantified sample, sample is placed on the 155 type vibrating sample magnetometers of Pinceton company product, the specific magnetising moment of measuring unit weight sample under the different externally-applied magnetic field intensity is the specific magnetising moment of sample, to add magneticstrength is X-coordinate, the sample specific magnetising moment is that ordinate zou is made curve, and the tangent slope of this curve by initial point is the initial susceptibility of this sample.
Being determined on the ASAP2400 static capacity absorption instrument of BET surface-area measured, and adsorption medium is a liquid nitrogen.
The activity of such catalysts surface-area refers to the hydrogen adsorption surface-area, on the Pulse Clemisorb2700 chemisorption instrument that Micromeritics company produces, measure, its measuring method is: the dress quantified sample places sample tube, at 50 ℃ of constant temperature, and made its drying in 8 hours with argon purge, be warming up to 250 ℃ and constant temperature and made its surface adsorption thing desorption in 2 hours, be cooled to 150 ℃ then, after treating temperature-stable, close argon gas, feed hydrogen, make sample inhale hydrogen 10 minutes, naturally cool to 50 ℃ then, with argon purge 1 hour, with the hydrogen that removes the sample surfaces physical adsorption and make detector count back zero, last heated sample to 300 ℃, when hydrogen began desorption, counter just had the numeral accumulation.The record last reading, adopt following calculation formula to try to achieve active surface area:
Example 29～30
When in technology provided by the invention, using high-ferromagnetic Ni-Fe-P catalyzer, can further reduce temperature of reaction, improve reaction velocity.
Catalyzer is the Ni of example 28 preparations
78.4-Fe
2-P
19.6High-ferromagnetic non-crystalline alloy catalyst, catalyzer uses separately, and consumption is 10 milliliters, and reaction raw materials and reaction conditions be with example 14, and just temperature of reaction is 100 ℃, magneticstrength 400.1Oe, reaction velocity are respectively 20 and 30h
-1, the results are shown in Table 7.
The presentation of results of table 7, in the technology provided by the invention, as adopt the Ni-Fe-P high-ferromagnetic non-crystalline alloy catalyst, and can further reduce temperature of reaction, improve reaction velocity, for example, example 29 is compared with example 14, and temperature of reaction has reduced by 50 ℃, and reaction velocity has improved 0.7 times, the bromine valency of product has but reduced by 53%, and the reaction velocity of the presentation of results technology provided by the invention of associative list 4 can be 2～40h
-1, best 4～30h
-1
Table 7
| Example number | Temperature of reaction ℃ | Reaction velocity h -1 | Product bromine valency g/100g |
| 29 30 | 100 100 | 20 30 | 0.25 0.42 |
Claims (9)
1. saturation hydrogenating process for removing olefines from reforming produced oil, comprise that reformed oil enters the magnetically stabilized bed reactor product through cooling off, separating by the bottom together with hydrogen after giving heat, tell product at last, it is characterized in that, in reactor, liquid reformate generates under oil and hydrogen and a kind of low temperature has activity, and has the hydrogenation catalyst contact of magnetic, it is solid magnetic stablizing bed to form gas-liquid, and the saturated hydrogenation reaction of alkene takes place.
2. technology according to claim 1 is characterized in that, the condition of hydrogenation reaction is 50～220 ℃ of temperature of reaction, reaction pressure 0.1～3MPa, reaction velocity 2～40h
-1, hydrogen-oil ratio 40～150.
3. technology according to claim 2 is characterized in that, the condition of hydrogenation reaction is 70～200 ℃ of temperature of reaction, reaction pressure 1～2MPa, reaction velocity 4～30h
-1, hydrogen-oil ratio 50～100.
4. technology according to claim 1, it is characterized in that, described catalyzer is to have ferromagnetic catalyzer, its ferromegnetism can be provided by the magnetic that catalyst themselves had, also can be by the method for mixing, adhesion, embedding, will have ferromagnetic material and non-magnetic catalyst activity component compound, be prepared into matrix material and make catalyzer have ferromegnetism.
5. technology according to claim 4 is characterized in that described catalyzer is meant Raney nickel catalyst.
6. technology according to claim 4 is characterized in that, described catalyzer is meant one or more the amorphous alloy catalyst that contains in chosen from Fe, cobalt, the nickel.
7. technology according to claim 6 is characterized in that, described catalyzer is meant nickel or cobalt or iron, the rare earth of 0～3 heavy % and the big surface amorphous alloy catalyst of Ni/Co/Fe-RE-P of surplus phosphorus that consists of 86～92.5 heavy %.
8. technology according to claim 7 is characterized in that, described catalyzer is meant the nickel that consists of 86～92.5 heavy %, the rare earth of 0～3 heavy % and the big surface amorphous alloy catalyst of Ni-RE-P of surplus phosphorus.
9. technology according to claim 6 is characterized in that, described catalyzer is meant the Ni that consists of 40～91 heavy %, the Fe of 2～40 heavy % and the Ni-Fe-P high-ferromagnetic non-crystalline alloy catalyst of surplus phosphorus.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101453C (en) * | 2000-08-22 | 2003-02-12 | 中国石油化工股份有限公司 | Hydrogenating denitrification catalyst and its preparing method |
| CN1132902C (en) * | 2000-08-22 | 2003-12-31 | 中国石油化工股份有限公司 | Hydrorefining catalyst |
| CN1307134C (en) * | 2004-02-18 | 2007-03-28 | 中国石油化工股份有限公司 | Process for removing less acetylene from ethylene fraction |
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| CN1068033C (en) * | 1998-10-13 | 2001-07-04 | 中国石油化工集团公司 | Saturated hydrogenation of olefin of reforming oil |
| CN1081222C (en) * | 1999-06-23 | 2002-03-20 | 中国石油化工集团公司 | Catalytic conversion process for reducing content of olefin in liquefied gas and gasoline |
| CN1087334C (en) * | 1999-06-16 | 2002-07-10 | 中国石化集团齐鲁石油化工公司 | Catalytic distillation selective hydrogenation process for cracking petroleum hydrocarbon vapor for producing C3 fraction composition |
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| CN102399589B (en) * | 2010-09-16 | 2014-04-30 | 中国石油化工股份有限公司 | Method for reducing content of olefin in reformate |
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| CN103285780B (en) * | 2012-02-24 | 2015-07-08 | 北京低碳清洁能源研究所 | Magnetic induction reactor of slurry bubble bed |
| CN103464059B (en) * | 2012-06-08 | 2015-05-13 | 北京低碳清洁能源研究所 | Methanation fluidization magnetron reactor system |
| CN106268883B (en) * | 2015-05-12 | 2019-02-01 | 中国石油化工股份有限公司 | A kind of preparation method of continuous reforming catalyst |
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| US4136016A (en) * | 1975-09-03 | 1979-01-23 | Exxon Research & Engineering Co. | Hydrocarbon conversion process utilizing a magnetic field in a fluidized bed of catalitic particles |
| US4235701A (en) * | 1979-03-30 | 1980-11-25 | Atlantic Richfield Company | Aromatics from dripolene |
| EP0556025A1 (en) * | 1992-02-10 | 1993-08-18 | Chemical Research & Licensing Company | Selective hydrogenation of C5 streams |
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| CN1101453C (en) * | 2000-08-22 | 2003-02-12 | 中国石油化工股份有限公司 | Hydrogenating denitrification catalyst and its preparing method |
| CN1132902C (en) * | 2000-08-22 | 2003-12-31 | 中国石油化工股份有限公司 | Hydrorefining catalyst |
| CN1307134C (en) * | 2004-02-18 | 2007-03-28 | 中国石油化工股份有限公司 | Process for removing less acetylene from ethylene fraction |
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| Publication number | Publication date |
|---|---|
| CN1152605A (en) | 1997-06-25 |
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