CN1433842A

CN1433842A - Gas-phase fluorinating method preparation for CoMo/TiQ2-Al2O3 dehydrogen desulfurization catalyst

Info

Publication number: CN1433842A
Application number: CN 02101986
Authority: CN
Inventors: 付贤智; 王绪绪; 凌岚; 翁浩; 杨青
Original assignee: Fuzhou University
Current assignee: Fuzhou University
Priority date: 2002-01-23
Filing date: 2002-01-23
Publication date: 2003-08-06
Anticipated expiration: 2022-01-23
Also published as: CN1150989C

Abstract

The present invention discloses a preparation method for modifying hydrodesulphurization catalyst used in processing petroleum product and raising catalytic activity. Said method utilizes the freon wet air to make fluooration treatment of catalyst carrier TiO2-Al2O3, then the cobalt and molybdenum active components are loaded on the fluorated carrier so as to obtain the invented catalyst. As compared with solution impregnation method said invention adopts the freon to make gas-phase fluoration preparation or catalyst, and has the advantages of that it is easy to control, uniform, does not damage structure of catalyst and can obviously raise activity of catalyst.

Description

CoMo/TiO 2-Al 2O 3The gaseous fluoridizing method preparation of Hydrobon catalyst

The present invention relates to the processing of oil product, specifically the Hydrobon catalyst that uses in the existing PETROLEUM PROCESSING is implemented modification, improve a kind of preparation method of catalytic activity.

Administering pollution, protecting environment is the significant problem that the our times various countries face jointly.In environmental pollution, the pollution of water and atmospheric environment is the most outstanding.In all pollution sources of water and atmosphere, chemical contamination is the most general.And in atmospheric environment was administered, oxysulfide was key objects because of causing acid rain, the vegeto-animal growth of destruction and corroding metal goods.Oxysulfide in the atmosphere mainly results from fuel engines institute exhaust gas discharged, but the source is an existing low amounts of organic sulfur thing in the fuel oil.Since the twentieth century, the global mobility vehicle sharply increases, and the consumption of vapour, diesel oil grows with each passing day, and the tail gas of engine emission can be on the rise to the pollution of environment, enters 21st century, and this situation can be more serious.Therefore, the basic outlet that reduces the atmospheric sulfer oxide contaminant is to remove and transform organic sulfur compound the fuel oil from the source, prepares eco-friendly clean fuel.

In recent years, developed countries such as U.S., moral, day, method all constantly propose strict restriction index to the quality, particularly sulfur content of fuel oil product in environmental legislation, require 2005 years to drop to 50ppm from present 300ppm.And also there is big gap in contrast to this in the quality of China's fuel oil product, and this is one of significant challenge that petrochemical enterprise in China is faced after the accession to WTO.Therefore, accelerate the development of China's oil chemical industry hydrotreatment technology, the quality that improves product has become the task of top priority.

It is exactly crucial process the PETROLEUM PROCESSING that the hydrotreatment process begins as the energy from oil, mainly refers to remove the various non-hydrocarbon component in the oil product, reduces the processing procedure of components such as sulfur-bearing, nitrogen in the oil product, comprises hydrodesulfurization, hydrodenitrogeneration etc.No matter hydrotreating catalyst passes by still is now heat subject in the catalyticing research always.The purpose of hydrotreatment process is to prevent the further catalyst poisoning of processing of oil product, reduces the discharging that causes air-polluting sulphur and nitrogen oxide, and the stability that improves oil product, prolongs the storage time.Along with the exhaustion of petroleum resources, the deep processing of petroleum resources and coal chemical develop rapidly and people to the improving constantly of environmental protection understanding of importance, the importance of hydrotreatment process will be more apparent outstanding in future.

Though the hydrotreating catalyst system of having reported is a lot, and some industrial process that also have been applied to, but the degree of depth of desulfurization, denitrogenation and stable aspect still unsatisfactory, so when seeking and developing new catalyst system and catalyzing, the modification or the improvement of existing catalyst is devoted in many researchs.

In hydrotreating catalyst, mix fluorine element, it is reported it is a kind of effectively method of modifying, but in all researchs in the past, what fluoridize was handled all employings is the ammonium fluoride solution infusion process, and the addition of fluorine is bigger, this once was proved and made the obvious negative effect that catalyst specific surface reduces and structure division destroys, and was difficult to reach the uniformity of fluoridizing.

Retrieval according to the interrelated data of Chinese patent shows, has not yet to see the relevant report that useful Organic fluoride chloride is handled Hydrobon catalyst.

The objective of the invention is to provide a kind of and existing Hydrobon catalyst is carried out fluorinated modified preparation method, thereby reach the purpose that improves catalyst hydrodesulfurization active with machine fluorochloride (fluorine Lyons).

The object of the present invention is achieved like this: a kind of CoMo/TiO ₂-Al ₂O ₃The gas phase fluorination modification preparation of Hydrobon catalyst is characterized in that: by the carrier TiO of fluorine Lyons humid air to catalyst ₂-Al ₂O ₃Carry out fluorination treatment, then on the carrier after fluoridizing again in the load cobalt and active component of cobalt make catalyst, specifically comprise:

Fluoridizing of carrier: used TiO ₂/ γ-Al ₂O ₃Carrier contains TiO ₂1～100% (quality); Used fluorization agent is fluorine Lyons (CFC-12 content is 99%).Described freon is diluted to the mist that contains variable concentrations and adds a certain amount of water vapour by bubbling with air, and wherein the concentration of freon is 1～10%; The gaseous mixture of fluorinated agent is by the fixed bed of loading catalyst carrier, and the flow velocity of gaseous mixture is 10～100cm ³/ min, the temperature of fixed bed is controlled at 200～500 ℃; When fluoridizing, generally keep 0.5～3h under these conditions, best 50～70min switches to flow of dried air again after the time, treats to take out the sample drying preservation after it drops to room temperature naturally.

Preparation of catalysts: CoMo/TiO ₂-Al ₂O ₃Active component cobalt and molybdenum are by conventional quantitatively immersion process for preparing in the catalyst.The TiO that fluoridized ₂-Al ₂O ₃Carrier is earlier with the ammonium molybdate solution dipping, at room temperature placement 10～12h and behind 120 ℃ of oven dry 4～8h, at 450～550 ℃ of roasting 2～5h.And then the dipping cobalt nitrate that uses the same method; MoO in made each goods ₃Be respectively 5～30% and 0.5～10% (weight) with CoO content.

Utilize fluorination process of the present invention also can directly carry out fluorination treatment, but its effect slightly is worse than the processing mode that first fluorinated support floods active component again to industrial catalyst.

The present invention adopts freon gas phase humid air fluoride process to replace villiaumite solution fluoridize method prepared catalyst that goes out under optimal conditions, and its BET specific area is 220～230m ²/ g; Its surface acidity is slightly than being lower than the catalyst of not fluoridizing; It is higher by 20～25% (at 310 ℃, 0.3g catalyst and 1.2cm than BY2 industrial catalyst to the hydrodesulfurization activity of thiophene ³Under/min thiophene the flow velocity).Therefore, compare, adopt fluorine Lyons that catalyst is carried out the gas phase fluorination tool and be easy to control, equal even advantages such as catalyst structure of not destroying with solution dipping method.So the present invention can reach the purpose of drafting.

Concrete preparation of the present invention and method are provided by following embodiment:

Take by weighing 8g by broken be 40～80 order particles and at the TiO of 500 ℃ of roasting 16h ₂-Al ₂O ₃Carrier, the diameter of packing into are in the glass tube of 30mm, and (20ml/min) rose to 420 ℃ with the speed of 5 ℃/min during first air in drying flowed, and switched to the fluorine Lyons mist that contains 1% volumetric concentration then.Mist enters before the carrier and adds steam through Bubbling method, and saturator constant temperature is at 25 ℃, overall flow rate 50cm ³/ min.Switch to flow of dried air at 420 ℃ again after keeping 1h, treat that it drops to naturally to take out sample after the room temperature and put into the drier preservation;

Take by weighing the carrier after 5g fluoridizes, carry out incipient impregnation, place 24h under the room temperature, 120 ℃ of air-dry 4h, 500 ℃ of calcining 6h with the ammonia solution (1.0ml/g) of ammonium molybdate; With with quadrat method dipping cobalt nitrate (0.9ml/g), promptly obtain fluorination catalyst.

Zhi Bei catalyst and BY2 industrial catalyst like this, with a fixed-bed catalytic reactor, at loaded catalyst 0.3g, the hydrogen mixed gas flow velocity 40cm of thiophene volumetric concentration 3% ³/ min, reaction temperature is 310 ℃ to be estimated down, and the conversion ratio of thiophene is respectively 43% and 32%.

Claims

1. CoMo/TiO ₂-Al ₂O ₃The gas phase fluorination modification preparation of Hydrobon catalyst is characterized in that: by the carrier TiO of fluorine Lyons humid air to catalyst ₂-Al ₂O ₃Carry out fluorination treatment, then on the carrier after fluoridizing again in the load cobalt and active component of cobalt make catalyst, specifically comprise:

Fluoridizing of carrier: used TiO ₂/ γ-Al ₂O ₃Carrier contains TiO ₂1～100%; Used fluorization agent is fluorine Lyons; Described freon is diluted to the mist that contains variable concentrations and adds a certain amount of water vapour by bubbling with air, the gaseous mixture of fluorinated agent is by the fixed bed of loading catalyst carrier, keep 0.5～3h when fluoridizing, 50～70min switches to flow of dried air again after the time, treat that it drops to take out after the room temperature naturally to put into the drier preservation;

Preparation of catalysts: CoMo/TiO ₂-Al ₂O ₃Active component cobalt and molybdenum are by conventional quantitatively immersion process for preparing, the TiO that fluoridized in the catalyst ₂-Al ₂O ₃Carrier is earlier with the ammonium molybdate solution dipping, at room temperature placement 10～12h and behind 120 ℃ of oven dry 4～8h, at 450～550 ℃ of roasting 2～5h; And then the dipping cobalt nitrate that uses the same method.

2. CoMo/TiO according to claim 1 ₂-Al ₂O ₃The gaseous fluoridizing method preparation of Hydrobon catalyst, it is characterized in that: the concentration of freon is 1～10%, the flow velocity of gas is 10～100cm ³/ min;

3. CoMo/TiO according to claim 1 ₂-Al ₂O ₃The gaseous fluoridizing method preparation of Hydrobon catalyst, its feature: the temperature that is fixed bed is controlled at 200～500 ℃;

4. CoMo/TiO according to claim 1 ₂-Al ₂O ₃The gaseous fluoridizing method preparation of Hydrobon catalyst, its feature: the MoO in made each goods ₃Be respectively 5～30% and 0.5～10wt% with CoO content.