CN1351116A - Hydrocatalyst and its preparing process - Google Patents

Abstract

A hydrocatalyst is prepared from alumina as carrier and metal component (Ni and Mo). It is suitable for hydrosaturating reaction of light oil, especially for hydrocracking light oil at 120-250 deg.C and 1-2.5 MPa to output aviation kerosene as jet fuel 3#.

Description

Hydrogenation catalyst and preparation method thereof

The present invention relates to a kind of hydrogenation catalyst and preparation method thereof, be used for the hydrogenation process of aromatic hydrocarbons and unsaturated hydrocarbons specifically, particularly be applicable to the Catalysts and its preparation method of the hydrogenation saturation history of producing qualified rocket engine fuel.

The subject matter of middle pressure hydrocracking technology is owing to the hydrogenation scarce capacity, and aromaticity content is higher in the boat coal cut, and smoke point is lower, and therefore in most cases, indexs such as boat coal component aromatic hydrocarbons that middle pressure hydrocracking produced and smoke point are defective.Influence dynamic of factor and thermodynamics two aspects of hydrogenation saturated activity in the hydrocracking process.From the kinetics angle, the activity of catalyst hydrogenation component is very high, but owing to is subjected to H ₂S, NH ₃And the influence of poisoning of impurity such as the organosulfur in the raw material, nitrogen, activity of such catalysts is suppressed, and the temperature of reaction that needs to improve catalyzer improves the hydrogenation reaction speed of catalyzer.In addition, middle pressure hydrocracking will be controlled certain cracking level, and this also needs higher temperature of reaction, but improve temperature of reaction the aromatic hydrocarbons saturated reaction is suppressed.Under condition of high voltage, the hydrogen dividing potential drop can remedy because temperature improves the influence that the aromatic hydrocarbons saturated reaction balance brought moves, but under middle press strip spare, the restriction of thermodynamic(al)equilibrium becomes principal element.

The high activated catalyst of industrial application generally speaking has two types at present, and a kind of is noble metal catalyst, and your the technology catalyzer as CN105363 introduces adopts Pt, Pd bimetallic catalyst.This catalyzer has good sulfur resistance and the saturated performance of aromatic hydrocarbons, at 250 ℃ of temperature of reaction, hydrogen pressure 3.0MPa, air speed 4.0h ^-1, under the reaction conditions of hydrogen to oil volume ratio 500, toluene conversion is 100%.This technology is owing to the less precious metal of employing raw material resources, so price is higher.Another kind is a nickel-alumina type catalyzer.This type of catalyst hydrogenation saturated activity is better, and cheap, and raw material resources are rich and easy to get, have wide practical use.CN891064476 introduces a kind of nickel aluminium oxide catalyst and preparation method thereof, this method is owing to adopted repeatedly technology such as dipping, low-temperature bake and low-temperature reduction, make catalyst activity increase, but because nickel content is higher, in preparation process, often need to adopt repeatedly dipping and repeatedly roasting, thereby this type of catalyst preparation process is comparatively complicated, cost is also higher.

Purpose of the present invention is exactly the defective that overcomes prior art, a kind of hydrogenation saturated activity height, good stability are provided, the catalyzer cost is low, the simple Catalysts and its preparation method of preparation flow, another object of the present invention is to overcome the defective that the middle pressure hydrocracking process is difficult to the qualified rocket engine fuel of direct production, adopt the highly active catalyzer of the present invention, reduce aromaticity content, improve smoke point, produce qualified rocket engine fuel.

Catalyzer of the present invention is in final catalyst weight, and molybdenum oxide content on catalyzer is 2～9%, and is best 3～6%, and nickel oxide content is 5～40%, is preferably 20～35%, and surplus is an aluminum oxide.The specific surface area of catalyzer is 100～250m ²/ g, pore volume are 0.20～0.35ml/g.

Preparation of catalysts method of the present invention is:

With aluminum oxide, molybdate compound, with after a kind of tackiness agent mixes, mixing moulding under 450-650 ℃ of air roasting 2-6 hour, makes carrier.

Above-mentioned carrier with dipping in basic solution that contains nickel compound or nickel nitrate solution 2-4 hour, is filtered under 100-180 ℃ of temperature dry 4-8 hour.

Repetition 2) operation 2～5 times.

With 3) product in air 200-350 ℃ following roasting 4-8 hour, can obtain catalyzer of the present invention.

Described aluminum oxide is a macroporous aluminium oxide, and its pore volume is 0.5-0.8ml/g, and specific surface area is 250-400m ²/ g as being 3824 macroporous aluminium oxides that Fushun No.3 Petroleum Factory catalyst plant is produced, also can be the V250 etc. of U.S.'s import.Molybdate compound can be ammonium molybdate, molybdic oxide etc.Described forming method is extrusion molding, and its shape can be trifolium-shaped or column.Tackiness agent can be common tackiness agent, as being little porous aluminum oxide (as the SB powder) and nitric acid or compositions such as sesbania powder and acetic acid.

Nickel compound containing can be nickelous nitrate or basic nickel carbonate, 1) in the step the best 500-600 of maturing temperature ℃, 3) in the best 240-320 of maturing temperature ℃.The number of times of dipping is decided by nickel content in the solution, for reducing the dipping number of times, contains basic solution or preferred its saturated solution of nickel nitrate solution of nickel compound.Catalyzer of the present invention also can adopt unsaturated pickling process or saturated immersion process for preparing.

When using catalyst treatment of the present invention to navigate coal, reaction conditions relaxes very much, and hydrogen pressure 1.0-2.5MPa, hydrogen to oil volume ratio are 50-400, and temperature of reaction 120-250 ℃, air speed 2.0-5.0h ^-1This catalyzer needs before use under hydrogen, and at 150-400 ℃, preferably 200-280 ℃ was reduced 4-10 hour down.

Hydrogenation catalyst of the present invention is carrier with the aluminum oxide, is active ingredient with metallic state and oxidation state nickel, and adds the molybdenum auxiliary agent.And the employing low-temperature bake is avoided the high-temperature roasting accumulation of metal, has reduced active component nickel and carrier interactions, compares with simple nickel-loaded catalyst, and activity is higher.Adopt this invention catalyzer, under demulcent reaction conditions comparatively, cooperate middle pressure hydrocracking technology direct production qualified 3 ^#Rocket engine fuel, thereby the practicality of raising middle pressure hydrocracking technology.Therefore both reduced energy consumption, reduced the requirement of reaction process again equipment, the insecurity of having avoided high top pressure operation to bring, simultaneously because the reaction process air speed is higher, remarkable in economical benefits.

Because this invention catalyzer is applicable to the hydrogenation saturated reaction process of the saturated or unsaturated hydrocarbons of aromatic hydrocarbons, particularly to handle middle pressure hydrocracking and produce the coal cut that navigates, the hydrogenation saturated activity is higher, can produce all qualified 3# rocket engine fuel of every index.Specific embodiment is as follows:

Embodiment

1) tackiness agent preparation:

Adopt SB powder 115 grams of German import to melt composite adhesives with 190ml 0.2M nitric acid glue.

2) preparing carriers:

Get import U.S. import V250 macroporous aluminium oxide 300 grams, 20 gram MoO ₃Mixing adds the above-mentioned tackiness agent of 150 grams, and mixing rolls, extrusion, and 110 ℃ of dryings 4 hours, 550 ℃ of roastings 5 hours, carrier is S-1.

(pore volume 0.75ml/g, specific surface area is 327m to get the macroporous aluminium oxide that Fushun No.3 Petroleum Factory catalyst plant produces respectively ²/ g) 320 grams, 270 restrain, and add MoO respectively ₃16 grams, 22 grams, mixing adds the above-mentioned tackiness agent of 190 grams, and mixing rolls, extrusion, 110 ℃ of dryings 4 hours, 530 ℃ of roastings 4 hours, carrier is S-2, S-3.

3) Preparation of Catalyst:

Get S-1, S-2, S-3 and respectively 100 restrain, dropped into nickelous carbonate saturated ammonia aqueous solution dipping 2 hours, filter, drying is 4 hours under 120 ℃.S-1 repeats 4 aforesaid operations, and S-2 repeats 2 aforesaid operations, and S-3 repeats 3 aforesaid operations.With the roasting 4 hours under 310 ℃ of air of the product of gained, can obtain catalyzer C-1 of the present invention, C-2, C-3.

Get S-1, S-2, each 100 gram of S-3, at NiNO ₃Soaked 2 hours in the saturated aqueous solution, filter, drying is 4 hours under 120 ℃.S-1 repeats 3 aforesaid operations, and S-2 repeats 4 aforesaid operations, and S-3 repeats 4 aforesaid operations.With the roasting 4 hours under 330 ℃ of air of the product of gained, can obtain catalyzer C-4 of the present invention, C-5, C-6.

Comparative example 1

Get U.S. import V250 macroporous aluminium oxide 330 gram, add 140 gram tackiness agents, mixing rolls, extrusion, and 100 ℃ of dryings 5 hours, 550 ℃ of roastings 4 hours, carrier is S-4.

Get S-4 120 gram, the nickel ammonia solution dipping in the use-case 42 hours filters, and 110 ℃ of dryings 4 hours repeat aforesaid operations, in order to reach the loading of NiO, can repeat aforesaid operations 4 times.With roasting under 330 ℃ of air of products therefrom 4 hours, can obtain C-7.Above-mentioned catalyst metal content sees Table 1

Application Example

Get C-1, C-2, C-3, C-4, C-5, C-6, four catalyzer of C-7 respectively, on the 200ml packaged unit, carry out activity rating, under hydrogen, activate 5 hours before estimating at 250 ℃.Employing rocket engine fuel that middle pressure hydrocracking produces is a raw material, and feedstock property sees Table 2, and activity rating the results are shown in Table 3.

Table 1 catalyst metal content table 2 stock oil main character

Catalyzer	??MoO 3??wt％	??NiO ??wt％	Pore volume ml/g	Specific surface area m 2/g
					C-1	??4.5	??29	??0.31	??180
C-2	??3.7	??24	??0.33	??240
					C-3	??5.1	??26	??0.25	??190
C-4	??4.3	??24	??0.28	??220
					C-5	??2.7	??31	??0.32	??207
C-6	??5.7	??31	??0.23	??170
					C-7	??0	??31	??0.38	??280

Stock oil	394V triumph VGO
		Density (20 ℃), g/cm 3	0.8173
Boiling range, ℃:	ASTM?D?86
		??IBP/10％	148/164
??30％/50％	179/198
		??70％/90％	219/244
??98％/FBP	261/263
		Freezing point, ℃	＜-60
Flash-point, ℃	39
		Smoke point, mm	18
Aromatic hydrocarbons, %	28

Table 3 evaluation result

Catalyzer	??C-1	??C-2	??C-3	??C-4	??C-5	??C-6	??C-7
								Processing condition:
The hydrogen dividing potential drop, MPa	??1.4	??2.0	??1.4	??1.4	??1.7	??1.3	??1.4
								Temperature of reaction, ℃	??130	??150	??130	??120	??120	??120	??120
Air speed, h -1	??2.0	??3.0	??2.0	??2.3	??2.5	??2.5	??2.5
								Hydrogen to oil volume ratio	??200	??400	??200	??300	??300	??300	??300
The rocket engine fuel product property:
								Density (20 ℃), g/cm 3	??0.8080	??0.8104	??0.8005	??0.8100	??0.8080	??0.8100	??0.8006
Boiling range, ℃: ASTM D 86
								IBP/10％	??147/164	??148/163	??150/164	??149/165	??147/164	??150/165	??151/166
30％/50％	??177/198	??178/200	??179/200	??180/199	??179/198	??180/199	??180/197
								70％/90％	??218/243	??218/241	??220/246	??210/245	??217/244	??219/246	??218/247
98％/FBP	??260/263	??256/261	??262/265	??261/263	??260/264	??261/265	??261/265
								Freezing point, ℃	??＜-60	??＜-60	??＜-60	??＜-60	??＜-60	??＜-60	??＜-60
Flash-point, ℃	??39	??42	??41	??42	??41	??39	??40
								Smoke point, mm	??28	??29	??25	??26	??28	??26	??22
Aromatic hydrocarbons, v%	??1.1	??5.9	??9.6	??8.0	??5.2	??7.9	??11

By table 3 finding as a result, adopt catalyzer of the present invention, the hydrogenation saturated activity is higher, but direct production 3# rocket engine fuel.

Claims (8)

1, a kind of hydrogenation catalyst contains molybdenum oxide 2～9% by weight, nickel oxide 5～40%, and surplus is an aluminum oxide, the specific surface area of catalyzer is 100～250m ²/ g, pore volume are 0.20～0.35ml/g.

2, according to the described catalyzer of claim 1, it is characterized in that described molybdenum oxide content is 3～6%, the content of nickel oxide is 20～35%.

3, a kind of right is wanted 1 described Preparation of catalysts method, and its process is:

(1) preparing carriers: with aluminum oxide, molybdate compound and after tackiness agent mixes, mixing moulding, under 450-650 ℃ of air roasting 2-6 hour;

(2) with above-mentioned carrier with soaking 2-4 hour in basic solution that contains nickel compound or the nickel nitrate solution, filter under 100-180 ℃ of temperature dry 4-8 hour;

(3) operation of repetition (2) is 2～5 times;

(4) with (3) product in air 200-350 ℃ following roasting 4-8 hour, can obtain catalyzer of the present invention.

4, in accordance with the method for claim 3, it is characterized in that the pore volume that described aluminum oxide is is 0.5-0.8ml/g, specific surface area is 250-400m ²/ g.

5, in accordance with the method for claim 3, it is characterized in that described nickel compound containing is selected from nickelous nitrate or basic nickel carbonate, molybdate compound is ammonium molybdate or molybdic oxide.

6, in accordance with the method for claim 3, it is characterized in that maturing temperature is 500-600 ℃ in the step (1), maturing temperature is 240-320 ℃ in the step (3).

7, in accordance with the method for claim 3, it is characterized in that described in the step (2) contain the nickel compound basic solution or nickel nitrate solution is its saturated solution.

8, a kind of boat coal hydrogenation treatment process is used the described catalyzer of claim 1, and processing condition are: hydrogen pressure 1.0-2.5MPa, hydrogen to oil volume ratio are 50-400, and temperature of reaction 120-250 ℃, air speed 2.0-5.0h ^-1