CN1302849A - Hydroactivity protector and its preparing process - Google Patents
Hydroactivity protector and its preparing process Download PDFInfo
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- CN1302849A CN1302849A CN 00110019 CN00110019A CN1302849A CN 1302849 A CN1302849 A CN 1302849A CN 00110019 CN00110019 CN 00110019 CN 00110019 A CN00110019 A CN 00110019A CN 1302849 A CN1302849 A CN 1302849A
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Abstract
A hydroactivity protector suitable for heavy raw oil with high contents of inferior S, N and metals has carrier containing gamma-alumina and delta-alumina, and contains the oxides of metals in families VIB, VIII and IA, and phosphorus. Its specific surface area is 100-250 sq.m/g and its porosity volume is 0.4-0.8 ml/g. It can prevent scaling, blocking and overdrop of pressure for catalyst bed, and elongate service life of hydrocatalyst.
Description
The present invention relates to a kind of protective material (hereinafter to be referred as protective material) and preparation method thereof with hydrogenation activity; A kind of hydrodemetallation (HDM) that can be applicable to heavy raw oil, hydrodesulfurization process protective material and preparation method thereof, particularly protective material of the stock oil hydrogenation deferrization process of high nitrogen-containing and preparation method thereof.
Exhaustion along with crude resources, the crude oil of refinery's processing both at home and abroad becomes day by day and heavily becomes bad, the viscous crude ratio increases, impurity such as colloid, bituminous matter and organometallic compound increase in the stock oil, especially naphthenic acid content is higher in some crude oil, and often the form with iron naphthenate concentrates in the heavy ends in storage or production process.The existence of these impurity is easy to make hydrofining, the hydrocracking catalyst inactivation or cause the fouling of full scale plant beds, obstruction, pressure drop is excessive and be forced to stop work.This is the problem that often runs in the industrial production, and one of effective way that solves this difficult problem is the protective material that has hydrogenation activity in the filling of hydrogenation catalyst top.
Protective material need have the ability of hydrodemetallation (HDM) and hold the ability of dirt, the catalyzer of relevant hydrodemetallation (HDM) has more report in patent documentation, for example at patent of invention CN1050736A, CN1052888A, CN1123309A, all reported the preparation method of Hydrodemetalation catalyst among the CN1123196A, they have common characteristic: the alumina supporter of selecting wide aperture, large pore volume, adopt VI B family or/and the VIII family metal oxide is an active ingredient, add alkali metal at least as auxiliary agent; In the preparing carriers process of catalyzer,, adopted various methods, but all adopted the mode of high-temperature roasting to obtain the carrier of wide aperture, large pore volume in order to obtain the carrier of wide aperture, large pore volume.These catalyst for demetalation have hydrodemetallation (HDM) effect preferably to the stock oil of general heavy raw oil, particularly high sulfur content; But the stock oil hydrodemetallation (HDM) effect for high nitrogen-containing is undesirable.
The object of the invention is to overcome the deficiencies in the prior art and shortcoming; develop a kind of hydrogenation protecting agent; this protective material not only has hydrodemetallation (HDM) effect preferably to the stock oil of high sulfur content; and the stock oil of high nitrogen-containing had ideal hydrodemetallation (HDM) effect equally; protective material particularly described in the invention; for metallic impurity such as the iron in the vacuum residuum of poor quality, alum, nickel, calcium, have stronger demetalization character and-oxygenation of Ding is desulphurizing activated.
Think in the document that having of sulphur is beneficial to the hydrodemetallation (HDM) reaction in the raw material, reaction has the inhibition effect and the existence of nitrogen is to hydrodemetallation (HDM), it is considered herein that reaction there is no promoter action to organosulfur to hydrodemetallation (HDM), only with H
2The S form exists, and the H in the duct of catalyzer
2S could have promoter action to the hydrodemetallation (HDM) reaction, and further thinks because H
2The existence of S can be played the inhibiting effect of offsetting nitrogen.Therefore among the present invention when the design Hydrodemetalation catalyst, make it have moderate hydrodesulfurization activity, thereby make and not only be applicable to high-sulfur stock oil by Hydrodemetalation catalyst provided by the invention, also be applicable to high-nitrogen raw oil.
Obtaining alumina supporter generally adopts its precursor pseudo-boehmite as material forming, roasting.The not high main formation activated alumina of maturing temperature is gama-alumina (γ-Al
2O
3), in the time of 500～800 ℃, begin by the activated alumina gama-alumina to δ-aluminum oxide (δ-Al
2O
3) transform, the optimum temps of being taked in the aforesaid patent of invention is all more than 800 ℃.The present invention requires to contain simultaneously in the alumina supporter gama-alumina and δ-aluminum oxide, therefore the maturing temperature scope is between 500～800 ℃, and selects the pseudo-boehmite of two kinds of different material route methods preparations also to help regulating the content of two kinds of aluminum oxide crystalline phases.
Technical characterictic of the present invention is earlier that the pseudo-boehmite with two kinds of different methods preparations mixes, peptization moulding, drying, roasting make the carrier that contains gama-alumina and δ-aluminum oxide simultaneously; Contain VI B family (Mo, W) metal oxide and VIII family (Fe, Co, Ni) metal oxide in the protective material as active ingredient, contain I A family metal oxide and/or V A family element as auxiliary agent.
It consists of by the protective material of method of the present invention preparation: the salic 68～95m% of being, and contain gama-alumina and δ-aluminum oxide in the alumina supporter simultaneously, contain VI B family metal oxide 3～22m% and VIII family metal oxide 0.5～5m%, contain I A family metal oxide 0～2m%, contain the element 0～3m% of V A family; Protectant pore structure is determined as by cryogenic nitrogen absorption (BET) method: specific surface 100～250m
2/ g, pore volume 0.4～0.8ml/g.Contain a certain amount of macropore in this catalyzer, measuring its pore volume by the suction method is 0.8～1.5ml/g.
Wherein VI B family metal oxide is preferably the oxide compound of Mo and/or W, and the group VIII metal oxide compound is preferably the oxide compound of Fe, Co, Ni or its mixture; I A family metal oxide is the oxide compound of Li, Na, K, Rb, Cs, is preferably potassium oxide; V A family element is P, As, Sb, Bi element, and best is P (phosphorus) element.
Consisting of of above-mentioned alumina supporter: contain γ-Al in the carrier simultaneously
2O
3And δ-Al
2O
3, γ-Al
2O
3Content be 5～95m%, δ-Al
2O
3Content be 95～5m%, wherein γ-Al
2O
3Content be preferably 30～70m%, δ-Al
2O
3Content be preferably 70～30m%; The pore structure of alumina supporter is determined as by cryogenic nitrogen absorption (BET) method: specific surface 150～300m
2/ g, pore volume 0.5～0.9ml/g.Contain a certain amount of macropore in this alumina supporter, measuring its pore volume by the suction method is 0.9～2.0ml/g.
The protectant concrete preparation process of hydrogenation activity of the present invention is: (1) with the pseudo-boehmite of two kinds of different material path of preparing mix, with the peptizing agent peptization, become with oil ammonia column
The moulding of type method makes alumina supporter, and drying is 1～10 hour between 100～130 ℃, 500～800
Roasting is 1～6 hour between ℃; (2) adopt the compound preparation dipping solution that contains the active ingredient element compound and/or contain auxiliary element; (3) adopt the solution in the step (2) to carry out disposable dipping the alumina supporter in the step (1), drying is 1～10 hour between 100～130 ℃, and roasting made protective material of the present invention in 1～6 hour between 400～700 ℃.
The pseudo-boehmite of two kinds of different material path of preparing described in the step (1), wherein a kind of pseudo-boehmite must be according to aluminum chloride-ammonia liquor neutralization process preparation; Another kind of pseudo-boehmite can be to be neutralized into the pseudo-boehmite of glue path of preparing according to sodium metaaluminate-Tai-Ace S 150 method or sodium metaaluminate-carbon dioxide process or sodium metaaluminate-nitrate method or sodium metaaluminate-aluminum nitrate method.Because the pseudo-boehmite of aluminum chloride-ammonia liquor neutralization process preparation has very strong adhesiveproperties, help improving the intensity of carrier.
Wherein aluminum chloride-ammonia liquor neutralization process refers to and adopts aluminum chloride and ammoniacal liquor to be neutralized into glue, filtration, washing and dry and pseudo-boehmite dry glue powder that make, presses that ordinary method gets final product in the document.
Wherein sodium metaaluminate-Tai-Ace S 150 method, sodium metaaluminate-carbon dioxide process, sodium metaaluminate-nitrate method, sodium metaaluminate-aluminum nitrate method refer to and adopt sodium metaaluminate and a kind of acid reagent to be neutralized into glue, filtration, washing and dry and pseudo-boehmite dry glue powder that make, press that ordinary method gets final product in the document; And this acid reagent can be Tai-Ace S 150 or carbon dioxide process or nitric acid or aluminum nitrate.
The content that the pseudo-boehmite of described two kinds of different material path of preparing is mixed in proportion the pseudo-boehmite that refers to aluminum chloride-ammonia liquor neutralization process preparation is that benchmark accounts for 10～40m% with the mass percent, and all the other are the amount of another kind of pseudo-boehmite.
The roasting 1～6 hour between 500～800 ℃ of said alumina supporter was preferably between 550～700 ℃ roasting 1～6 hour.
Described oil ammonia column forming method can be referring to patent CN1068975A.Adopt oil ammonia column to form and be beneficial to the carrier that keeps and form large pore volume, and extruded moulding or extrusion molding process often make the large pore volume loss because of squeezing action.
Described peptizing agent can be a mineral acid, for example nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid etc., or organic acid, for example acetic acid, oxalic acid, citric acid etc., or acid Soluble Anions aluminium salt, for example aluminum chloride, aluminum nitrate, Tai-Ace S 150 etc. also can be that the mixing of above-mentioned several peptizing agents is used, and for example use nitric acid and acetic acid as peptizing agent simultaneously.The peptizing agent consumption has difference because of adopting different peptizing agents and different alumina supporter forming methods, can realize (can referring to patent CN1068975A) according to the ordinary method of introducing in the document; For example, be mixed with the false colloidal sol of aluminium hydroxide earlier, drip the method for ball forming then if adopt, when with nitric acid being the false colloidal sol of peptizing agent preparation aluminium hydroxide, aluminium hydroxide is Al (OH) with the ratio of the amount of substance of nitric acid
3: HNO
3Get final product between=20～100: 1 scope.
Described auxiliary agent is meant I A family (Li, Na, K, Rb, Cs) metal oxide and/or V A family element, and wherein best is potassium oxide and phosphorus.
Described active ingredient is meant VI B family (Mo, W) and VIII family (Fe, Co, Ni) metal oxide, active ingredient is benchmark with the catalyst quality, contain VI B family metal oxide 3-22m% and VIII family metal oxide 0.5-5m%, wherein the oxide compound of molybdenum and nickel preferably.
Dipping solution compound method described in the hydrogenation protecting agent preparation process (2) refers to adopt and contains VI B family (Mo, W) element compound, contain VIII family (Fe, Co, Ni) element compound, contains I A family (Li, Na, K, Rb, Cs) metallic element compound, contains V A family (P, As, Sb, Bi) element compound and solubility promoter (such as ammoniacal liquor) and add in the entry dissolving and can prepare, so contain active ingredient and auxiliary agent simultaneously in the dipping solution that the present invention prepares.For example: (1) takes by weighing required ammonium molybdate, basic nickel carbonate, phosphoric acid (or ammonium phosphate) and saltpetre, measures the mixing of ammoniacal liquor and water and can be mixed with the mixing solutions that contains potassium, phosphorus, molybdenum and nickel; (2) take by weighing required ammonium metawolframate, nickelous nitrate, phosphoric acid (or ammonium phosphate) and saltpetre, measure the water mixing and can be mixed with the mixing solutions that contains potassium, phosphorus, tungsten and nickel.Phosphate builder wherein can derive from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate etc., and potassium promoter can derive from saltpetre, salt of wormwood, potassium oxalate, Potassium ethanoate etc.
Described dipping refers to saturated dipping or supersaturation dipping (being also referred to as excessive dipping), saturated pickling process is meant puts into a rotating container to alumina supporter, under the condition of rotating the dipping solution of carrier saturated extent of adsorption is vaporific and is sprayed onto on the carrier; The supersaturation pickling process refers to the solution impregnation of 1.2～3.0 times of volumes of carrier saturated extent of adsorption 0.5～2.0 hour.No matter adopt above the sort of mode to flood, all only carry out disposable dipping.
Owing to adopt alumina supporter not only to contain gama-alumina but also contain δ-aluminum oxide among the present invention; add active metal component and auxiliary agent on the carrier again stock oil is had certain hydrogenation desulfurization and denitrogenation effect; therefore by the hydrogenation protecting agent of the present invention's preparation, not only be suitable for high-sulfur stock oil but also be fit to high-nitrogen raw oil.This protective material has certain desulfurization performance and ideal metal removal effect, and this protective material can hold heavy metal, coke parent (colloid), bituminous matter, condensed-nuclei aromatics and organometallic compound.This protective material be suitable for doing high sulfur content stock oil protective material, be suitable for doing the protective material of high nitrogen-containing stock oil; The heavy raw oil that is suitable for doing the high metal content of the high nitrogen of high-sulfur inferior also comprises the protective material of vacuum residuum.Load protective material provided by the invention on hydrogenation catalyst top; can make this device processing heavy raw oil inferior; can effectively solve the fouling of industrial hydrogenation unit beds, obstruction, pressure drop is excessive and the problem of being forced to stop work, and prolongs the work-ing life of hydrogenation catalyst.
Further describe and illustrate advantage of the present invention, technical characterictic and protectant preparation process below by embodiment, but should not think that the present invention only was confined to this.
Embodiment 1-5
Take by weighing the pseudo-boehmite dry glue powder (being called for short the A pseudo-boehmite) of a certain amount of aluminum chloride-ammonia liquor neutralization process preparation and the pseudo-boehmite 1000g of sodium metaaluminate-Tai-Ace S 150 method preparation, the salpeter solution 500ml and the 1000ml water that add 0.69mol/l stir into false colloidal sol, on the oil ammonia column balling head, drip ball, wet rubber ball is following dry 8 hours at 110 ℃, 650 ℃ of following roastings 3 hours, make ball-aluminium oxide carrier A, B, C, D; Other takes by weighing pseudo-boehmite dry glue powder (the being called for short the A pseudo-boehmite) 500g of aluminum chloride-ammonia liquor neutralization process preparation and the pseudo-boehmite 1000g of sodium metaaluminate-carbon dioxide process preparation, the acetum 550ml and the 1000ml water that add 0.75mol/l stir into false colloidal sol, on the oil ammonia column balling head, drip ball, wet rubber ball is following dry 4 hours at 120 ℃, 550 ℃ of following roastings 5 hours, make ball-aluminium oxide carrier E, its prepared every kind of carrier granularity is two kinds of φ 1.3～2.4mm and φ 3.0～5.5mm, adopt the suction method to measure the pore volume of carrier, adopt cryogenic nitrogen absorption (BET) method to measure the pore structure of carrier, wherein list the character that granularity is φ 1.3～2.4mm carrier in the table 1.
The preparation condition of table 1 alumina supporter and character
| Embodiment | ????1 | ????2 | ????3 | ????4 | ????5 |
| Bearer number A pseudo-boehmite add-on, the total pore volume of g, ml/g (suction method) pore volume, the ml/g specific surface, m 2/ g tap density, g/ml intensity, N/mm | ????A ????200 ???1.73 ???0.65 ????210 ???0.34 ????11 | ????B ???300 ??1.54 ??0.69 ???218 ??0.37 ????17 | ????C ???350 ??1.31 ??0.71 ???220 ??0.42 ???18 | ????D ???400 ??1.11 ??0.76 ???214 ??0.44 ???23 | ????E ???500 ??0.90 ??0.72 ???221 ??0.51 ???41 |
Embodiment 6
Take the unfired alumina supporter of the method preparation among embodiment 1 and the embodiment 2, roasting carrier under different temperature and times adopts cryogenic nitrogen absorption (BET) method to measure the pore structure of carrier to the carrier of different roasting conditions respectively then; The product of roasting of pseudo-boehmite mainly is γ-Al
2O
3And δ-Al
2O
3Two kinds of crystalline phases, the degree of crystallinity in the present embodiment are meant that certain aluminum oxide crystalline phase accounts for the mass percent of sample total amount, adopt Japanese X-ray diffractometer of science to measure γ-Al in the carrier
2O
3Degree of crystallinity, surplus be δ-Al
2O
3Degree of crystallinity, the results are shown in table 2.
The physico-chemical property of carrier under the different roasting conditions of table 2
| Carrier | Maturing temperature ℃ | Time hr | ??γ-Al 2O 3Degree of crystallinity, m% | ???δ-Al 2O 3Degree of crystallinity, m% | Pore volume ml/g | Specific surface area, aperture m 2/g???????nm |
| ??A ??A ??A ??A ??A ??B ??B | ??500 ??550 ??600 ??700 ??750 ??600 ??700 | ???5.0 ???4.0 ???3.0 ???3.0 ???2.0 ???3.0 ???3.0 | ????95 ????82 ????57 ????35 ????10 ????51 ????36 | ???????5 ??????18 ??????43 ??????65 ??????90 ??????49 ??????64 | ??0.73 ??0.72 ??0.71 ??0.61 ??0.58 ??0.73 ??0.63 | ??265???????11.0 ??255???????11.3 ??238???????11.9 ??196???????12.6 ??171???????13.5 ??253???????11.4 ??201???????12.7 |
Found through experiments raising along with maturing temperature; the aperture of carrier increases; crossing low maturing temperature mainly is that activated alumina is a gama-alumina; and too high maturing temperature mainly forms δ-aluminum oxide; control maturing temperature in the present invention between 500～800 ℃ of scopes; can make and both contain gama-alumina in the carrier; contain δ-aluminum oxide again; because certain activity aluminum oxide; make protective material have certain hydrodesulfurization activity; can promote demetallated ability, also can offset the restraining effect of nitrogen in the raw material simultaneously.
Embodiment 7-11
Introduced protectant preparation process.Take by weighing that granularity is the ball type carrier of φ 1.3～2.4mm among a certain amount of embodiment 1-5, with Ammonium Heptamolybdate ((NH
4)
6Mo
7O
244H
2O, technical grade, Fushun Chemical Plant produces), nickelous nitrate (Ni (NO
3)
26H
2O, technical grade, Fushun Chemical Plant produces), auxiliary agent (H
3PO
4(content 85%) and/or KNO
3) and ammonia soln (concentration is 5.9mol/l) be mixed with dipping solution; Calculate the amount of required dipping solution by the water-absorbent of carrier, once spray, in 120 ℃ of dryings 3 hours, roasting then, can be protected agent A-1, B-1, C-1, D-1, E-1, protectant composition and physico-chemical property see Table 3.
Table 3
| Embodiment | ???7 | ????8 | ????9 | ????10 | ????11 | ||
| The protective material numbering | ?A-1 | ?B-1 | ?C-1 | ?D-1 | ?E-1 | ||
| Carrier, numbering | ?A | ?B | ?C | ?D | ?E | ||
| The carrier consumption, g | ?500 | ?500 | ?300 | ?300 | ?300 | ||
| Nickelous nitrate, g | ?43.3 | ?16.6 | ?31.6 | ?61.0 | ?51.4 | ||
| Ammonium molybdate, g | ?51.7 | ?25.1 | ?66.8 | ?93.2 | ?106 | ||
| The protective material preparation | Auxiliary agent (H 3PO 4),ml | ??- | ?5.6 | ?11.9 | ?7.9 | ?15.8 | |
| Auxiliary agent (KNO 3),g | ??- | ?4.8 | ???- | ?3.5 | ?5.8 | ||
| Ammonia volume, ml | ?568 | ?699 | ?315 | ?290 | ?290 | ||
| Maturing temperature, ℃ | ?450 | ?500 | ?540 | ?580 | ?650 | ||
| Roasting time, hr | ?6 | ?4 | ?4 | ?3 | ?2 | ||
| Protective material is formed and character: | |||||||
| Al 2O 3 | ????m％ | 89.5 | ?94.2 | ?77.3 | ?74.1 | ?70.5 | |
| MoO 3 | ????m％ | 8.3 | ?4.0 | ?16.4 | ?19.5 | ?21.9 | |
| NiO | ????m％ | 2.1 | ?0.8 | ?4.2 | ?4.1 | ?3.5 | |
| K 2O | ????m％ | - | ?0.4 | ?- | ?1.1 | ?1.8 | |
| P | ????m％ | ?0.5 | ?1.5 | ?0.9 | ?2.1 | ||
| Total pore volume (suction method), ml/g | 1.19 | ?1.21 | ?0.91 | ?0.84 | ?0.88 | ||
| Pore volume surface-area aperture intensity | ??ml/g ??m 2/g ??nm ??N/mm | ??0.68 ???214 ??12.6 ???12 | ???0.64 ????221 ???11.6 ????12 | ????0.51 ?????179 ????11.3 ?????35 | ???0.53 ????165 ???12.9 ????28 | ??0.51 ???160 ??12.9 ???26 |
Embodiment 12
Get the protective material A-1 among the embodiment 7, estimate on 200ml fixed bed hydrogenation device, appreciation condition is: reaction stagnation pressure 15.7Mpa, hydrogen-oil ratio 400 (v/v), volume space velocity 9.5h
-1Use Middle East Saudi Arabia high-sulfur VGO as stock oil.Stock oil character is listed in table 4, and evaluation result is listed in table 5.
Table 4 stock oil character
| The stock oil title | Saudi Arabia VGO |
| Density (20 ℃), kg/m 3Boiling range, ℃ | ???914 |
| Initial boiling point | ???298 |
| ???????????????10％ | ???372 |
| ???????????????50％ | ???452 |
| ???????????????90％ | ???525 |
| Final boiling point | ???565 |
| Nitrogen, ppm | ???979 |
| Sulphur, m% | ???2.41 |
| Iron, ppm | ???2.69 |
Table 5 protective material evaluation result
| Temperature of reaction, ℃ | ???350 | ???360 |
| Generate oily sulphur content m% | ???1.00 | ???0.74 |
| Desulfurization degree % | ???58.5 | ???69.3 |
| Generate oily iron level ppm | ???0.39 | ???0.23 |
| Deferrization rate % | ???85.5 | ???91.4 |
Present embodiment shows that by the protective material of the present invention preparation the stock oil of high sulfur content is had certain sweetening effectiveness, deferrization effective.
Embodiment 13
Get the protective material C-1 among the embodiment 9, estimate on 200ml fixed bed hydrogenation device, appreciation condition is: reaction stagnation pressure 15.7MPa, hydrogen-oil ratio 400 (v/v), volume space velocity 9.5h
-1Adopt high nitrogen high ferro isolated island decompressed wax oil as stock oil, stock oil character is listed in table 6, and evaluation result is listed in table 7.
Table 6 stock oil character
| The stock oil title | Isolated island VGO |
| Density (20 ℃), kg/m 3 | ????909 |
| Boiling range, ℃ | |
| Initial boiling point | ????319 |
| ????10％ | ????369 |
| ????50％ | ????421 |
| ????90％ | ????467 |
| Final boiling point | ????506 |
| Nitrogen ppm | ???1846 |
| Sulphur m% | ???0.78 |
| Iron ppm | ????70 |
Table 7 protective material evaluation test result
| Temperature of reaction, ℃ | ??350 | ??360 |
| Generate oily sulphur content, m% | ???0.17 | ???0.14 |
| Desulfurization degree, % | ???78.2 | ???82.0 |
| Generate oily iron level, ppm | ???0.47 | ???0.35 |
| The deferrization rate, % | ???99.3 | ???99.5 |
Present embodiment shows that by the protective material of the present invention preparation the stock oil of high nitrogen is had higher deferrization sweetening effectiveness; The deferrization rate is 82%, and desulfurization degree is 99.5%.
Embodiment 12 and 13 shows the protective material that is prepared by the present invention to high-sulfur stock oil, and high-nitrogen raw oil all has ideal deferrization effect, and this protective material can be used for doing in the hydrogenation unit protective material, guarantees the normal operation of downstream hydrogenation catalyst.
Embodiment 14
The protective material D-1 that gets embodiment 10 is on the 200ml hydrogenation unit, and adopting isolated island vacuum residuum inferior is that raw material carries out activity rating, processing condition: hydrogen dividing potential drop 14.7MPa, volume space velocity 10h
-1, hydrogen-oil ratio (V/V) 1000,380 ℃ of temperature.Stock oil character and evaluation result are listed in table 8.
Table 8 stock oil character and evaluation result
| Raw material and product | Isolated island vacuum residuum | Product |
| Nitrogen content, ppm | ?????7480 | ?????- |
| Sulphur content, m% | ?????2.56 | ?????1.24 |
| Desulfurization degree, % | ?????51.5 | |
| Nickel content, ppm | ?????42.2 | ?????20.8 |
| The nickel removal rate, % | ?????50.8 | |
| Content of vanadium, ppm | ?????4.40 | ?????2.28 |
| Vanadium removal rate, % | ?????48.2 | |
| Calcium contents, ppm | ?????23.6 | ?????16.2 |
| The decalcification rate, % | ?????31.4 | |
| Iron-holder, ppm | ?????14.3 | ?????4.01 |
| The deferrization rate, % | ?????71.9 |
Present embodiment shows that the protective material by the present invention's preparation has desulfurization preferably, nickel removal, vanadium removal effect to vacuum residuum inferior, and especially deferrization is effective.Reaction result is: this protectant desulfurization degree is 51%, and the nickel removal rate is 50.8%, and vanadium removal rate is 48%, and the deferrization rate is 71.9%.
Claims (16)
1. hydrogenation activity protective material; it consists of: salic is 68～95m%; and contain gama-alumina and δ-aluminum oxide in the alumina supporter simultaneously; contain VI B family metal oxide 3～22m% and VIII family metal oxide 0.5～5m%; contain I A family metal oxide 0～2m%, contain the element 0～3m% of V A family.
2. according to the described protective material of claim 1, its pore structure is determined as by low-temperature nitrogen adsorption method: specific surface 100～250m
2/ g, pore volume 0.4～0.8ml/g.
3. according to the described protective material of claim 2, measuring its pore volume by the suction method is 0.8～1.5ml/g.
4. according to the described protective material of claim 1, wherein VI B family metal oxide is the oxide compound of Mo, W, and the group VIII metal oxide compound is the oxide compound of Fe, Co, Ni; I A family metal oxide is the oxide compound of Li, Na, K, Rb, Cs; V A family element is P, As, Sb, Bi element.
5. according to the described protective material of claim 4, wherein said I A family metal oxide is K
2O, V A family element is P.
6. according to the described protective material of claim l, wherein consisting of of alumina supporter: γ-Al
2O
3Content be 5～95m%, δ-Al
2O
3Content be 95～5m%.
7. according to claim 1 or 6 described protective materials, wherein consisting of of alumina supporter: γ-Al
2O
3Content be 30～70m%, δ-Al
2O
3Content be 70～30m%.
8. according to the described protective material of claim 1, wherein the pore structure of alumina supporter is determined as by low-temperature nitrogen adsorption method: specific surface 150～300m
2/ g, pore volume 0.5～0.9ml/g contains a certain amount of macropore in this alumina supporter, and measuring its pore volume by the suction method is 0.9～2.0ml/g.
9. protectant preparation method of hydrogenation activity: (1) with the pseudo-boehmite of two kinds of different material path of preparing mix, with the peptizing agent peptization, use oil ammonia column
The forming method moulding makes alumina supporter, and drying is 1～10 hour between 100～130 ℃,
Roasting is 1～6 hour between 500～800 ℃; (2) adopt the compound preparation dipping solution that contains the active ingredient element compound and/or contain auxiliary element; (3) adopt the solution in the step (2) to carry out disposable dipping the alumina supporter in the step (1), dry, roasting makes protective material of the present invention.
10. according to the described preparation method of claim 9, wherein the pseudo-boehmite of two kinds of different material path of preparing described in the step (1) is a kind of according to aluminum chloride-ammonia liquor neutralization process preparation; Another kind is neutralized into the glue path of preparing according to sodium metaaluminate-Tai-Ace S 150 method or sodium metaaluminate-carbon dioxide process or sodium metaaluminate-nitrate method or sodium metaaluminate-aluminum nitrate method.
11. according to the described preparation method of claim 9, wherein the blending ratio of the pseudo-boehmite of two kinds of different material path of preparing is that the content of the pseudo-boehmite of aluminum chloride-ammonia liquor neutralization process preparation is that benchmark accounts for 10～40m% with the mass percent, and all the other are the amount of another kind of pseudo-boehmite.
12. according to the described preparation method of claim 9, the roasting 1～6 hour between 500～800 ℃ of wherein said alumina supporter is roasting between 550～700 ℃ 1～6 hour.
13. according to the described preparation method of claim 9, wherein auxiliary agent is meant I A family metal oxide and/or V A family element.
14. according to the described preparation method of claim 13, wherein said I A family metal oxide is a potassium oxide, V A family element is a phosphorus.
15. according to the described preparation method of claim 9, wherein active ingredient is meant VI B family and VIII family metal oxide, active ingredient is benchmark with the catalyst quality, contains VI B family metal oxide 3-22m% and VIII family metal oxide 0.5-5m%.
16. according to the described preparation method of claim 15, wherein VI B family metal oxide is the oxide compound of Mo and/or W, the VIII family metal oxide is the oxide compound of Fe, Co, Ni or its mixture.
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| CN00110019A CN1101452C (en) | 2000-01-04 | 2000-01-04 | Hydroactivity protector and its preparing process |
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| CN00110019A CN1101452C (en) | 2000-01-04 | 2000-01-04 | Hydroactivity protector and its preparing process |
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| CN1101452C CN1101452C (en) | 2003-02-12 |
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| CN1047957C (en) * | 1994-10-19 | 2000-01-05 | 中国石油化工总公司抚顺石油化工研究院 | Prepn of alumina supporter |
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| CN1101452C (en) | 2003-02-12 |
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