CN103240106A

CN103240106A - Preparation method of wax oil hydrogenation pretreatment refining agent

Info

Publication number: CN103240106A
Application number: CN2013101972241A
Authority: CN
Inventors: 石芳; 杨建国; 于海斌; 张国辉; 肖寒; 赵训志; 钟读乐; 李佳
Original assignee: China National Offshore Oil Corp CNOOC; CNOOC Energy Technology and Services Ltd; CNOOC Tianjin Chemical Research and Design Institute Co Ltd
Current assignee: China National Offshore Oil Corp CNOOC; CNOOC Energy Technology and Services Ltd; CNOOC Tianjin Chemical Research and Design Institute Co Ltd
Priority date: 2013-05-24
Filing date: 2013-05-24
Publication date: 2013-08-14

Abstract

The invention relates to a preparation method of a wax oil hydrogenation pretreatment refining agent; and the preparation method is characterized by comprising the steps of: adding zirconium hydroxide and silica sol into macroporous aluminum hydroxide dry gel powder; drying and carrying out high-temperature roasting to obtain silicon-zirconium modified aluminum oxide gamma-Al2O3 as carrier; and loading active hydrogenated metal oxide components such as tungsten, molybdenum, cobalt and nickel as well as auxiliary agents containing components such as phosphorus and fluorine by using an impregnation method.

Description

A kind of preparation method of wax oil hydrogenation preliminary treatment finishing agent

Technical field

The invention belongs to the oil refining field, be specifically related to a kind of preparation method of wax oil preliminary treatment Hydrobon catalyst.Be specially with silicon modified zirconia aluminium oxide is the preparation method of the wax oil preliminary treatment Hydrobon catalyst of carrier.

Background technology

Traditional fraction oil Hydrobon catalyst selects for use zirconia, silica-alumina to make carrier usually.The active metal component of load is selected from VI B family and group VIII metal usually, and bimetallic component or three metal group of being made up of Co, Ni, Mo, W commonly used are graded.Be main fraction oil hydrofinishing for desulfurization, the preferred Co of hydrogenation active metals component (Ni) of catalyst-Mo combination; Be hydrogenated to main fraction oil hydrofinishing, preferred Ni-W combination for denitrogenation, aromatic hydrocarbons are saturated etc.

CN1289828A discloses γ-Al ₂O ₃Or to contain SiO ₂γ-Al ₂O ₃Be the Hydrobon catalyst of carrier, catalyst is active component with W, Mo, Ni, P.With SiO ₂The Al of modification ₂O ₃For the performance of the hydrogenation catalyst of carrier can necessarily be improved, but its pore structure is undeveloped, and content of metal is not high, and carrier acid amount is lower, and its middle strong acidity center is less, is unfavorable for the open loop fracture of azacyclo-, and denitrification effect is not obvious.

Adopt a kind of highly active hydrogenation catalyst that has in the petroleum hydrocarbon hydrotreating method that USP4880524 proposes.This catalyst is Ni-Mo/Al ₂O ₃Type, specific area is greater than 300m ²/ g, less than the aperture of 7nm greater than 70%.This catalyst has hydrofinishing activity preferably for light ends oil, but the reactive metal of its load is two kinds of components of Ni, Mo, and the problem that metal dispersity is lower is difficult for solving.Just present domestic price, molybdenum oxide is than tungsten oxide price height, WO ₂Be about 250,000 yuan/ton, MoO ₃Be 440,000 yuan/ton, therefore for domestic oil refining enterprises, adopt Ni-Mo/Al ₂O ₃The type catalyst can increase production cost.The high-activity hydrofining catalyst of exploitation W-Ni-Mo three metal components is conducive to reduce domestic catalyst production cost.

In the whole bag of tricks of decompressed wax oil lighting, wax oil hydrogenation-catalytic cracking combined technique is a kind of good method.Wax oil is after the hydrogenation preliminary treatment, remove impurity such as most sulphur, nitrogen, and saturated part aromatic hydrocarbons, improved hydrogen content, arene content and sulphur nitrogen content have been reduced, to alleviate nitride to the murder by poisoning of follow-up catalytic cracking or hydrocracking catalyst, the crackability energy of wax tailings is provided, and raising catalytic cracking conversion ratio, the fecund light-end products produced coke less, and product quality is improved significantly, wherein the sulfur content in the gasoline products reduces significantly, and content of olefin in gasoline and diesel cetane-number all make moderate progress.Simultaneously, the low-sulfur diesel-oil of by-product about 15% has improved the diesel and gasoline ratio of full factory in the wax oil hydrogenation preprocessing process.Therefore, the technology as catalytically cracked material obtains more and more general application after the wax oil hydrogenation preliminary treatment.

Summary of the invention

The objective of the invention is on the basis of existing technology, a kind of wax oil hydrogenation prerefining Preparation of catalysts method that reaches higher desulfurization removing nitric activity with relatively low cost is provided.

The catalyst of the present invention's preparation, the alumina support of use silicon modification, i.e. SiO ₂-ZrO ₂-γ-Al ₂O ₃Complex carrier is with γ-Al ₂O ₃Be skeleton structure, introduce SiO ₂Improve the middle strong acidity of carrier, the activated centre number of C-N scission of link is increased, introduce ZrO ₂Make carrier surface have flourishing pore structure, active component Mo, Ni, W are evenly distributed in the catalyst, have improved the utilization rate of reactive metal.

The present invention adopts complexing technology preparation maceration extract, and complexing agent can be monoethanolamine or citric acid etc., reactive metal is evenly distributed on carrier and has higher decentralization; And compare with the agent of existing industrial W-Ni-Mo reference, have higher hydrodesulfurization, denitrification activity.

Aluminium oxide precursor in the catalyst carrier for hydrgenating of the present invention is the macropore boehmite, and additive comprises expanding agent, extrusion aid, can use as required.

The present invention is the preparation method of the pre-Hydrobon catalyst of a kind of wax oil, it is characterized in that: add zirconium hydroxide and Ludox, silicon modified zirconia aluminium oxide γ-A1 that drying, high-temperature roasting make by a kind of macropore aluminum hydroxide solid elastomer powder ₂O ₃Be carrier, adopt infusion process supported active hydrogenation metal oxide component tungsten, molybdenum, Cobalt, nickel and auxiliary agent phosphorous, fluorine component thereof to constitute again;

Weight content in the described silicon modified zirconia alumina support: zirconia is 8～15wt%, and silica is 6～20wt%, and the drying condition of carrier is 80～200 ℃ of down dry 2～20h, and roasting condition is at 450～700 ℃ of following roasting 1～8h; The weight content that described hydrogenation metal oxide accounts for catalyst is nickel oxide 1～15wt%, molybdenum oxide 2～12 wt%, tungsten oxide 12～35wt%; The weight content that auxiliary agent phosphorous, fluorine component accounts for catalyst is phosphorus pentoxide 1～7wt%, adds fluorine content 1～9wt% in the ammonium fluoride mode; Adopt complexing technology preparation maceration extract, complexing agent is monoethanolamine or citric acid; The complexing agent addition is the 2-8% of hydrogenation metal compound weight content; Dipping back baking temperature is normal temperature～120 ℃, drying time 1～24h, 400～550 ℃ of sintering temperatures, roasting time 1～8h makes product catalyst;

Pore volume ≮ the 0.2mL/g of prepared catalyst, specific area is ≮ 130m ²/ g, mechanical strength ≮ 15N/mm.

According to preparation method of the present invention, it is characterized in that the carrier sintering temperature is 500～600 ℃; The weight content that described hydrogenation metal oxide accounts for catalyst is nickel oxide 3～10 wt%, molybdenum oxide 2～10 wt%, tungsten oxide 18～30wt%; Dipping back baking temperature is 80～120 ℃, drying time 4～24h, 420～530 ℃ of sintering temperatures, roasting time 1～6h,

According to preparation method of the present invention; It is characterized in that; The application of catalyst in the pre-hydrofinishing at wax oil after the presulfurization, wax oil comprises normal pressure wax oil, wax tailings, and normal pressure diesel oil, catalytic diesel oil in the light wax oil; Operating condition when catalyst is used is: reaction pressure 5～15MPa, 300～450 ℃ of reaction temperatures, volume space velocity 0.5～3.0h during liquid ^-1, hydrogen to oil volume ratio 500～1000.

The invention discloses a kind of preparation method of wax oil hydrogenation catalyst for refining, the catalyst that this method makes uses the aluminium oxide of silicon modified zirconia to be carrier, has both good surface texture and surface acid property; Adopt the complexing infusion process, reactive metal is evenly distributed on carrier and have higher decentralization; Reactive metal is selected group VIB metal molybdenum, tungsten and VIII family nickel for use, constitutes three metal components, and adds auxiliary agent phosphorous, fluorine component.The catalyst that this method makes has excellent hydrodesulfurization, hydrodenitrogeneration performance and aromatic hydrocarbons saturability to the wax oil of the high nitrogen of high-sulfur.

The specific embodiment

The percentage that following examples relate to all is weight percentage.

Embodiment 1

Present embodiment is comparative example.By a kind of macropore aluminum hydroxide solid elastomer powder 240g, its alumina content is 70%, sesbania powder 6g, 66% red fuming nitric acid (RFNA) 9g, and methylcellulose 10g, add deionized water, in kneader, mediate mixing, by the banded extruder extruded moulding, obtain little of the clover of diameter 1.5mm.Drying is 12 hours in 120 ℃ of baking ovens, and the blowing air roasting is 4 hours in 500 ℃ of tube furnaces, gets alumina support T1, and its character sees Table 1.

Getting little 140g of the alumina support that makes is added to and contains 55g six hydration ammonium metatungstates, 24g four hydration ammonium heptamolybdates, in the 100 mL deionized water solutions of Nickelous nitrate hexahydrate 35g and 7g citric acid, dipping is 4 hours under the room temperature, after the separation, wet catalyst is placed in 120 ℃ of baking ovens, dry 4 hours, 500 ℃ of roastings of blowing air are 4 hours in the tube furnace, get catalyst A, and its character sees Table 2.

Embodiment 2

By a kind of macropore aluminum hydroxide solid elastomer powder 240g, its alumina content is 70%, sneak into zirconium hydroxide 40g, 25% Ludox 55g, sesbania powder 6g, 66% red fuming nitric acid (RFNA) 9g and methylcellulose 10g, add deionized water, in kneader, mediate mixing, by the banded extruder extruded moulding, obtain little of the clover of diameter 1.5 mm.120 ℃ of baking oven inner dryings 12 hours, 550 ℃ of roastings of blowing air were 4 hours in tube furnace, get silicon modified zirconia alumina support T2, and its character sees Table 1.

Little the 140g of silicon modified zirconia alumina support that makes be added to contain 48g six hydration ammonium metatungstates, 20g four hydration ammonium heptamolybdates, in the 100 mL deionized water solutions of 25g Nickelous nitrate hexahydrate, 8g phosphoric acid and 6g citric acid, dipping is 4 hours under the room temperature, after the separation, wet catalyst is placed in 120 ℃ of baking ovens, dry 4 hours, 500 ℃ of roastings of blowing air are 4 hours in the tube furnace, get catalyst B, and its character sees Table 2.

Embodiment 3

By a kind of macropore aluminum hydroxide solid elastomer powder 240 grams, its alumina content is 70%, sneak into zirconium hydroxide 45g, 25% Ludox 65g, sesbania powder 6g, 66% red fuming nitric acid (RFNA) 9g and polyethylene glycol (degree of polymerization 2000) 10g, add deionized water, in kneader, mediate mixing, by the banded extruder extruded moulding, obtain little of the clover of diameter 1.5mm.120 ℃ of dryings are 12 hours in baking oven, and 550 ℃ of roastings of blowing air are 4 hours in tube furnace, and the character of gained silicon modified zirconia alumina support T3 sees Table 1.

In 15 gram ammonium fluorides, add deionized water to 200mL, after the dissolving, add little of 140g silicon modified zirconia alumina support, dipping is 4 hours under the room temperature, after the separation, 120 ℃ of baking oven inner dryings 4 hours, the fluoro-containing alumina of strip was made in logical dry air roasting 4 hours in 500 ℃ tube furnace again wet fluoro-containing alumina bar.Behind little cool to room temperature of fluoro-containing alumina, be added in the 100mL deionized water solution that contains 50g six hydration ammonium metatungstates, 22g four hydration ammonium heptamolybdates, 27g Nickelous nitrate hexahydrate and 6g phosphoric acid, 7g citric acid, dipping is 4 hours under the room temperature, after the separation, wet catalyst is placed in 120 ℃ of baking ovens, and dry 4 hours, 500 ℃ of roastings of blowing air were 4 hours in the tube furnace, obtain catalyst C, this catalyst property sees Table 2.

Table 1

Table 2

Embodiment 4-6

This example illustrates that catalyst provided by the invention is for the hydrogenation prerefining performance of wax oil.

The evaluation feedstock oil that adopts is the Zhoushan coking light wax oil that is provided by Zhong Hai Zhoushan petrochemical industry.

Adopt the fixed bed hydrogenation device of 200mL respectively catalyst A, B, C to be carried out hydrogenation reaction performance evaluation.

Presulfiding of catalyst condition: use to contain 3%CS ₂The boat coal, with air speed 1.0h ^-1, hydrogen to oil volume ratio 500:1 under the operating pressure of 8.0MPa, carries out presulfurization to catalyst, and pre-vulcanization process is as follows.

Advance presulfurization oil under 120 ℃, behind the oil-feed 2h, constant temperature vulcanizes 2 h; Begin to heat up, be warming up to 150 ℃ with 15 ℃/h, constant temperature vulcanizes 4 h; Be warming up to 230 ℃ with 6 ℃/h, constant temperature vulcanizes 10 h; Be warming up to 290 ℃ with 6 ℃/h, constant temperature vulcanizes 6 h; Be warming up to 340 ℃ with 10 ℃/h, constant temperature vulcanizes 6 h; At last be cooled to 200 ℃ naturally, presulfurization finishes.

The evaluation response condition is: operating pressure 8.5 MPa, and 380 ℃ of reaction temperatures, hydrogen to oil volume ratio 820:1, volume space velocity are 1.2h ^-1Evaluation result sees Table 3.

Evaluation result in the table 3 shows, at pressure 8.5 MPa, and 380 ℃ of temperature, hydrogen-oil ratio is 820:1, volume space velocity is 1.2 h ^-1Process conditions under, catalyst of the present invention is to refining higher desulfurization, denitrogenation and the deolefination activity of demonstrating of wax oil hydrogenation.Adopt technology such as zirconium silicon modified support and reaming modulation, make catalyst C have higher hydrofinishing effect than A, B.

Table 3

Claims

1. the preparation method of the pre-Hydrobon catalyst of wax oil is characterized in that: add zirconium hydroxide and Ludox, silicon modified zirconia aluminium oxide γ-A1 that the drying high-temperature roasting makes by a kind of macropore aluminum hydroxide solid elastomer powder ₂O ₃Be carrier, adopt infusion process supported active hydrogenation metal oxide component tungsten, molybdenum, Cobalt, nickel and auxiliary agent phosphorous, fluorine component thereof to constitute again;

Weight content L zirconia is 8～15wt% in the described silicon modified zirconia alumina support, and silica is 6～20wt%, and the drying condition of carrier is 80～200 ℃ of down dry 2～20h, and roasting condition is at 450～700 ℃ of following roasting 1～8h; The weight content that described hydrogenation metal oxide accounts for catalyst is nickel oxide 1～15wt%, molybdenum oxide 2～12 wt%, tungsten oxide 12～35wt%; The weight content that auxiliary agent phosphorous, fluorine component accounts for catalyst is phosphorus pentoxide 1～7wt%, adds fluorine content 1～9wt% in the ammonium fluoride mode; Adopt complexing technology preparation maceration extract, complexing agent is monoethanolamine or citric acid; The complexing agent addition is the 2-8% of hydrogenation metal compound weight content; Dipping back baking temperature is normal temperature～120 ℃, drying time 1～24h, 400～550 ℃ of sintering temperatures, roasting time 1～8h makes product catalyst;

2. according to the described preparation method of claim 1, it is characterized in that the carrier sintering temperature is 500～600 ℃; The weight content of described hydrogenation metal oxide is nickel oxide 3～10 wt%, molybdenum oxide 2～10 wt%, tungsten oxide 18～30wt%; Dipping back baking temperature is 80～120 ℃, drying time 4～24h, 420～530 ℃ of sintering temperatures, roasting time 1～6h.

3. according to claim 1 or 2 described preparation methods; It is characterized in that; The application of catalyst in the pre-hydrofinishing at wax oil after the presulfurization, wax oil comprises normal pressure wax oil, wax tailings, and normal pressure diesel oil, catalytic diesel oil in the light wax oil; Operating condition when catalyst is used is: reaction pressure 5～15MPa, 300～450 ℃ of reaction temperatures, volume space velocity 0.5～3.0h during liquid ^-1, hydrogen to oil volume ratio 500～1000.