CN105642335B - A kind of hydrocracking catalyst and preparation method thereof - Google Patents

Abstract

The present invention discloses a kind of preparation method of hydrocracking catalyst, including following content：（1）Prepare carrier of hydrocracking catalyst；（2）Salting liquid is prepared, impregnation steps are saturated（1）Then the carrier of hydrocracking catalyst of preparation is dried, roasts；（3）It is saturated impregnation steps with liquefied olefines（2）Catalyst after the roasting of acquisition so that carbon distribution reaction occurs on catalyst, carbon deposition catalyst is made；（4）By step（3）The carbon deposition catalyst carrier of preparation is directly added into the advance Muffle kiln roasting for being warming up to 400 ~ 600 DEG C 5 ~ 200 minutes, burn off catalyst carrier surface layer carbon distribution；（5）Active metal salt solution is prepared, impregnation steps are saturated（4）Carrier after roasting obtains hydrocracking catalyst finished product after drying, roasting.Hydrocracking catalyst prepared by this method can carry out selective hydrogenation to crackate heavy naphtha and tail oil, both reduced the hydrogen consumption of device, and can also produce the heavy naphtha and tail oil product of high quality simultaneously.

Description

A kind of hydrocracking catalyst and preparation method thereof

Technical field

The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, relates in particular to a kind of chemical industry type and hydrogen is added to split Change catalyst and preparation method thereof.

Background technology

As crude quality becomes weight, variation year by year, environmental regulation is increasingly stringent, and market is continuous to the demand of clear gusoline Increase so that the hydrogen addition technology for producing clean fuel is more and more widely used.In the secondary operation technology of crude oil, evaporate Point oily hydrocracking technology have the characteristics that strong adaptability to raw material, production operation and products scheme flexibility greatly, good product quality, Various heavys, inferior raw material can be converted into the high-quality jet fuel of market in urgent need, diesel oil, lube basestocks and Chemical industry naphtha and tail oil preparing ethylene by steam cracking raw material etc. play product distribution and product quality tune in full factory's production procedure The effect for saving device is the core that " oil-change-fibre " combines, it has also become most important heavy oil in modern times oil refining and petro chemical industry One of deep processing technique.From nineteen fifty-nine Chevron company Isocracking hydrocracking technology for the first time in California, USA Ritchie Since covering oil plant commercial Application, the development and application of hydrocracking technology obtains swift and violent development.CLG companies, UOP are public External major refining such as department, Criterion catalyst Co.s, Albemarle companies, Haldor Topsoe companies and Axens companies Oily company and R＆D institution increase the input of technological innovation, and significant progress is obtained in terms of hydrocracking technology exploitation.It cuts Only 2012, the global total working ability of hydrocracking unit reached 2.78Mt/a or more, accounts for crude oil time processing ability 6.26%。

China is one of the country for grasping distillate hydrocracking technology earliest in the world, is early in last century the fifties Distillate hydrocracking technology is started to develop, and is voluntarily set using the complete set technology of oneself domestic exploitation in the sixties in last century Count China's first set distillate hydrocracking device that has been constructed and put into operation.In the 21st century, is with rapid development of economy, oil production The demand rapid growth of product, China Petroleum consumption reaches 4.67 hundred million tons within 2012, occupies second place of the world.At the same time, China It is hydrocracked working ability and also obtains swift and violent development, throughput has reached 60.0Mt/a, accounts for crude oil time processing energy Nearly the 12% of power is far above world average level.However China's hydrocracking technology application market develops and is unevenly distributed weighing apparatus, locates Reason ability is concentrated mainly on state-owned large-scale oil refining enterprise, and the technological process of use is more single, and most tail oil products are as ethylene Cracking stock.As crude oil in China quality becomes weight, variation year by year, the processing capacity of sour crude increases year by year, and environmental protection is to refining oil work Skill itself and petroleum product-quality require increasingly stringent, lasting increasing of the market to clean fuel oil and high-quality chemical industry raw materials requirement amount Long, hydrocracking technology will be also more widely applied at home, and market competition will be growing more intense, while also pair plus hydrogen is split Change technical merit to put forward higher requirements.

The core of hydrocracking technology is hydrocracking catalyst, technology the carrying dependent on catalyst performance of technology It rises.Hydrocracking catalyst is bifunctional catalyst, including adding dehydrogenation functionality and cracking function.Usual cracking function is carried by acidity Body component provides, and includes mainly molecular sieve and amorphous oxide.And dehydrogenation functionality is added mainly to be provided by hydrogenation metal, add hydrogen golden Category generally comprises conventional non-noble metal components, such as W, Mo, Ni, Co, and noble metal is typically chosen Pt, Pa.It is hydrocracked and urges Incorporation way generally use kneading method, beating method, coprecipitation method and the infusion process etc. of non-noble metal components in agent, wherein with dipping Method is the most commonly used, accounts for 80% or more existing commercial Application hydrocracking catalyst.Infusion process prepares hydrocracking catalyst, system Standby range request hydrogenation metal salt of crossing can make that stability is good, highly concentrated metal salt solution.Hydrocracking catalyst category In fine chemical product, preparation process is complicated, and production process is restricted by many factors.The hydrogenation activity of hydrocracking catalyst The metal component in VI B races in the periodic table of elements and VIII race, most widely used is in tetra- kinds of metals of W, Mo, Ni, Co It is one or more of.Wherein metallic nickel（Or metallic cobalt）It is the most common metal promoter component of hydrocracking catalyst.In order to ensure The materialization of hydrocracking catalyst and catalytic performance require the metallic salt introduced to be removed after Roasting Decomposition in its preparation process Outside oxygen element, no other element residuals.When preparing hydrocracking catalyst using infusion process and coprecipitation method, it is also necessary to configure The metal salt solution that concentration is high, stability is good.Nickel metal（Or cobalt）Salt in, nitrate has that solubility is high, solution is steady After qualitative good, decomposition the advantages that noresidue, it is widely used in hydrocracking catalyst preparation process.Patent CN96109702.7 provides a kind of co-impregnated solution preparing high-activity hydrocracking catalyst, is helped by ammonium metatungstate, nickel nitrate one kind Preserved material is obtained bright with carrier prepared catalyst performance of the co-impregnated solution dipping containing Y type molecular sieve, refractory inorganic oxides Aobvious promotion.Patent CN88103069.4 gives a kind of preparation method of supported non-noble metal hydrocracking catalyst, Active component is VI B races and/or VIII B races non-noble metal j element in the periodic table of elements, and metal incorporation way is mainly using leaching Stain method.Middle distillate selectivity of product remains unchanged when there is the catalyst of preparation reaction temperature to increase, gas generates in product Amount less, coking situation the characteristics of being similar to using conventional molecular sieve as acidic components catalyst, suitable for mild hydrocracking.Patent US5,229,347 give a kind of preparation method of hydrocracking catalyst, and it includes VIB and VIII groups that this, which prepares catalyst, Metal component is closed, after catalyst carrier molding, metal component is introduced using infusion process, dipping rear catalyst is by dry, roasting The step of burning, prepares finished catalyst.

Hydrocracking technology has strong adaptability to raw material, production operation and the big, good product quality of products scheme flexibility etc. Various heavy inferiors can be fed high-quality jet fuel, diesel oil, the lube basestocks for being converted into market in urgent need by feature And chemical industry naphtha and tail oil preparing ethylene by steam cracking raw material, it has also become modern times oil refining and petro chemical industry are most important heavy One of oily deep processing technique, at home and abroad obtains increasingly extensive application.Hydrocracking process includes cracking and plus hydrogen two On the one hand process carries out cracking to heavy raw oil and is converted into light fraction oil ingredient, on the other hand carried out while cracking Add hydrogen, to improve product quality.But some hydrogenation processes are that we are not intended to see, such as are hydrocracked dress in chemical industry type The hydrocracking process set, product is mainly heavy naphtha and tail oil, respectively as the reaction of reformer and ethylene unit Charging.Hydrocracking process adds the requirement of hydrogen to be different heavy naphtha and tail oil, and the heavy naphtha that cracking generates adds The virtue that hydrogen can reduce heavy naphtha is latent, this is unfavorable for reformer.And the tail oil part as feed ethylene plus hydrogen then The arene content in tail oil is advantageously reduced, is conducive to improve ethylene unit yield and operation cycle, and existing is hydrocracked There is no solve the above problems catalyst well.

Invention content

In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of hydrocracking catalyst, prepared by this method Hydrocracking catalyst can carry out selective hydrogenation to crackate heavy naphtha and tail oil, both reduce the hydrogen of device Consumption, can also produce the heavy naphtha and tail oil product of high quality simultaneously.

A kind of preparation method of hydrocracking catalyst, including following content：

（1）Selective hydrocracking catalyst carrier material, carrier material include at least one acid cracking material, and acid is added Property peptizing agent prepares carrier of hydrocracking catalyst through molding, drying and roasting；

（2）The salting liquid that active metallic content is 10 ~ 30g/100ml is prepared, impregnation steps are saturated（1）Prepare plus hydrogen is split Change catalyst carrier, is then dried, roasts；

（3）It is saturated impregnation steps with liquefied olefines（2）Catalyst after the roasting of acquisition adds for 50 ~ 400 DEG C in the air stream 1 ~ 70h of heat so that carbon distribution reaction occurs on catalyst, carbon deposition catalyst is made；

（4）By step（3）The carbon deposition catalyst carrier of preparation is directly added into be warming up in 400 ~ 600 DEG C of Muffle furnace in advance Roasting 5 ~ 200 minutes, burn off catalyst carrier surface layer carbon distribution so that carrier inside carbon deposition quantity account for total carbon deposition quantity before roasting 10% ~ 90%；

（5）The salting liquid that active metallic content is 40 ~ 80g/100ml is prepared, impregnation steps are saturated（4）Load after roasting Body obtains hydrocracking catalyst finished product after drying, roasting.

The method of the present invention step（1）Described in acid cracking material include molecular sieve and amorphous acidic components, molecule Sieve generally comprises Y type molecular sieve, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve, one kind in MCM-41 molecular sieves or several Kind, amorphous acidic components are generally one or more of amorphous silica-alumina, amorphous silicon magnesium, clay etc., in all acid Preferred Y type molecular sieve in property alphang materials.Required molecular sieve can require to carry out suitable modification according to performance.It is described Carrier of hydrocracking catalyst material further include inorganic refractory oxide, generally aluminium oxide or aluminium oxide containing auxiliary agent, use When generally using aluminum hydroxide solid elastomer powder as raw material.There is macropore in amorphous acidic components and the preferred this field of aluminium oxide Hold, the raw material of bigger serface.

The method of the present invention step（1）It is middle that the aqueous solution of nitric acid that mass fraction is 3 ~ 30% is added as peptizing agent, drying condition For in 80 ~ 120 DEG C of dry 1 ~ 5h, roasting condition is to roast 1 ~ 5h at 400 ~ 500 DEG C.

The method of the present invention step（2）Or step（5）Described in active metal can be the VIIIth race in the periodic table of elements And/or the VIth race's metallic element, the VIIIth race's active metal are Ni, the VIth race's active metal is to be W and/or Mo；Including inclined The salts such as ammonium tungstate, ammonium molybdate, nickel nitrate, basic nickel carbonate, nickel acetate, molybdenum trioxide and oxide, preferably W-Ni combine or Mo-Ni is combined.

The method of the present invention step（3）The alkene can be the positive structure of carbon atom number 2 ~ 10 or alkene, the diene of isomery Hydrocarbon, preferably hexadiene, nhepene.

The method of the present invention step（4）By step（3）The carbon deposition catalyst carrier of preparation is directly added into and is warming up to 450 in advance ~ 550 DEG C of Muffle kiln roasting 20 ~ 150 minutes, burn off catalyst carrier surface layer carbon distribution so that carrier inside carbon deposition quantity accounts for step （3）The 40 ~ 80% of total carbon deposition quantity.

The method of the present invention step（5）The hydrogenation catalyst finished product, specific surface area are 200 ~ 400m²/ g, Kong Rongwei 0.2 ~ 0.5ml/g, 30 ~ 90wt% containing acid material in carrier, preferably 40 ~ 70wt%, surplus are aluminium oxide, carrier and work in catalyst Property metal mass content be respectively 55 ~ 85% and 15 ~ 45%, the VIIIth race's active metallic content be 3 ~ 15%.

Hydrocracking catalyst prepared by the method for the present invention can improve the matter of heavy naphtha and hydrocracking tail oil simultaneously Amount reduces hydrogen consumption, is a kind of excellent chemical industry type hydrocracking catalyst.

Specific implementation mode

The functions and effects further illustrated the present invention with reference to embodiment, but following embodiment is not constituted to this hair The limitation of bright method.The Y type molecular sieve used in the embodiment of the present invention is according to 2 side of patent CN200710012075.1 embodiments It is prepared by method.

Embodiment 1

（1）The macroporous aluminium oxide of the Y molecular sieve and dry weight 250g that take dry weight 150g after mixing, is added 3g/100ml dust technologies 200ml is rolled, then extruded moulding through 120 DEG C of dry 4h, obtains carrier after 550 DEG C of roasting 3h, compiles Number be T-1；（2）Configure W-Ni maceration extracts：1000ml dippings are configured after taking ammonium metatungstate 241g and nickel nitrate 240g to be dissolved in water Solution, active metal is with WO in gained dipping solution₃It is respectively 20g/100ml and 6g/100ml with NiO content calculations, number is RY-1；It takes T-1 300g to impregnate 2h in 600ml RY-1, then, takes out carrier room temperature and dry in the air 100 DEG C of dry 4h after 2h processed, 500 DEG C roasting 3h obtain low-metal content carrier, number CTL-1；（3）It takes CTL-1 300g to be positioned in 600ml hexadiene solvents to soak Then stain 4h is directly placed into after air atmosphere heats the abundant carbon distributions of 15h at 150 DEG C and is previously heated in 450 DEG C of Muffle furnace Roasting 30 minutes, obtains CTL-2, and CTL-2 carrier insides carbon deposition quantity is 60% of total carbon deposition quantity before its roasting；（4）Configure high concentration W-Ni dipping solutions：1000ml dipping solutions, gained dipping are configured after taking ammonium metatungstate 482g and nickel nitrate 480g to be dissolved in water Active metal is with WO in solution₃It is respectively 40g/100ml and 12g/100ml, number RY-2 with NiO content calculations；It is right 300gCTL-2 carries out saturation dipping, then, final catalyst CT-1 is obtained after 100 DEG C of dry 3h, 500 DEG C of roasting 3h.In CT-1 Active metal W O₃It is respectively 24% and 7% with NiO contents, evaluation procedure is listed in 1 ~ table of table 3 with result

Embodiment 2

（1）The macroporous aluminium oxide of the Y molecular sieve and dry weight 200g that take dry weight 200g after mixing, is added 3g/100ml dust technologies 200ml is rolled, then extruded moulding through 120 DEG C of dry 4h, obtains carrier after 550 DEG C of roasting 3h, compiles Number be T-2；（2）Configure W-Ni maceration extracts：1000ml dippings are configured after taking ammonium metatungstate 241g and nickel nitrate 240g to be dissolved in water Solution, active metal is with WO in gained dipping solution₃It is respectively 20g/100ml and 6g/100ml with NiO content calculations, number is RY-3；It takes T-2 300g to impregnate 2h in 600ml RY-3, then, takes out carrier room temperature and dry in the air 100 DEG C of dry 4h after 2h processed, 500 DEG C roasting 3h obtain low-metal content carrier, number CTL-3；（3）It takes CTL-3 300g to be positioned in 600ml nhepene solvents to soak Then stain 4h is directly placed into after 200 DEG C of heating abundant carbon distributions of 20h is previously heated in 500 DEG C of Muffle furnace in air atmosphere Roasting 40 minutes, obtains CTL-4, and CTL-4 carrier insides carbon deposition quantity roasts 50 % of preceding total carbon deposition quantity for it；（4）It configures highly concentrated Spend W-Ni dipping solutions：1000ml dipping solutions, gained leaching are configured after taking ammonium metatungstate 482g and nickel nitrate 480g to be dissolved in water Active metal is with WO in stain solution₃It is respectively 36g/100ml and 12g/100ml, number RY-4 with NiO content calculations；It is right 300gCTL-4 carries out saturation dipping, then, final catalyst CT-2 is obtained after 100 DEG C of dry 4h, 500 DEG C of roasting 4h.In CT-2 Active metal W O₃It is respectively 23% and 7.2% with NiO contents, evaluation procedure is listed in 1 ~ table of table 3 with result.

Comparative example 1

Carrier selects T-1 carrier 30 as one kind 0g in embodiment 1, adjustment W, Ni active metal impregnation concentration to control WO₃Contain with NiO Amount is respectively 35g/100ml and 10g/100ml, and after supersaturation impregnates 2h, dry, roasting obtains comparative example catalyst, number The upper active metal W O of BCT-1, BCT-1₃It is respectively 24.2% and 7.1% with NiO contents, evaluation result is listed in 1 ~ table of table 3.

Comparative example 2

Without step（3）Hexadiene impregnation process, remaining prepares sample activity tenor WO with embodiment 1₃With NiO contents are respectively 24.2% and 7.1%, and evaluation procedure is listed in 1 ~ table of table 3 with result.

The reactivity worth of catalyst is prepared with comparative example 1 ~ 2 in order to investigate embodiment 1 ~ 2, to catalyst on midget plant Evaluation test is carried out, evaluating apparatus is using single hop series connection intermediate oil complete alternation flow production heavy naphtha and is hydrocracked Tail oil, an anti-filling regular refiner catalyst, two anti-load respectively are urged according to prepared by embodiment 1 ~ 2 and 1 ~ 2 method of comparative example Agent, evaluation result are listed in 1 ~ table of table 3.

1 raw material oil nature of table

1 ~ 2 used operating condition of 2 embodiment 1 ~ 2 of table and comparative example

3 embodiment 1 ~ 2 of table and 1 ~ 2 evaluation result of comparative example

Show using present invention side by using embodiment 1 and contrast test of 1 catalyst of comparative example on evaluating apparatus Catalyst prepared by method is compared with the equally distributed hydrocracking catalyst of active metal prepared using conventional method, tail oil production Product BMCI values are lower, and scheelite virtue is dived and significantly improved, and chemical hydrogen consumption significantly declines.It is sent out by embodiment 2 and the comparison of comparative example 2 Catalysis existing, that catalyst prepared by the method for the present invention was once incrementally distributed from inside to outside with the active metal conventionally prepared Agent is compared, and shows better effect, and scheelite virtue is dived higher, and chemical hydrogen consumption is lower, and BMCI values are substantially reduced, this and this hair The catalyst carrier interior surface carbon distribution occupy-place of bright use prevents secondary high concentration active metal dipping process active metal to urging Diffusion is related inside agent, and the uneven distribution of catalyst activity metal can be preferably formed using the method for the present invention, therefore, Show better reactivity worth.

Claims (12)

1. a kind of preparation method of hydrocracking catalyst, it is characterised in that：Including following content：

（1）Selective hydrocracking catalyst carrier material, carrier material include at least one acid cracking material, and Aci-Jel is added Solvent prepares carrier of hydrocracking catalyst through molding, drying and roasting；

（2）The salting liquid that active metallic content is 10 ~ 30g/100ml is prepared, impregnation steps are saturated（1）Being hydrocracked for preparing is urged Then agent carrier is dried, roasts；

（3）It is saturated impregnation steps with liquefied olefines（2）Catalyst after the roasting of acquisition, in the air stream 50 ~ 400 DEG C heating 1 ~ 70h so that carbon distribution reaction occurs on catalyst, carbon deposition catalyst is made；

（4）By step（3）The carbon deposition catalyst carrier of preparation is directly added into the advance Muffle kiln roasting for being warming up to 400 ~ 600 DEG C 5 ~ 200 minutes, burn off catalyst carrier surface layer carbon distribution so that carrier inside carbon deposition quantity accounts for the 10% ~ 90% of the preceding total carbon deposition quantity of roasting；

（5）The salting liquid that active metallic content is 40 ~ 80g/100ml is prepared, impregnation steps are saturated（4）Carrier after roasting, warp Hydrocracking catalyst finished product is obtained after dry, roasting.

2. according to the method described in claim 1, it is characterized in that：Step（1）Described in acid cracking material include molecule Sieve and amorphous acidic components.

3. according to the method described in claim 2, it is characterized in that：Molecular sieve includes Y type molecular sieve, beta-molecular sieve, ZSM-5 point One or more of sub- sieve, SAPO molecular sieve, MCM-41 molecular sieves.

4. according to the method described in claim 2, it is characterized in that：Amorphous acidic components are amorphous silica-alumina, amorphous silicon One or more of magnesium, clay.

5. according to the method described in claim 1, it is characterized in that：Step（1）In acid cracking material be Y type molecular sieve.

6. according to the method described in claim 1, it is characterized in that：Step（1）Described in carrier of hydrocracking catalyst material Material includes inorganic refractory oxide, is aluminium oxide or aluminium oxide containing auxiliary agent, use is using aluminum hydroxide solid elastomer powder as raw material.

7. according to the method described in claim 1, it is characterized in that：Step（1）The middle nitric acid aqueous solution that mass fraction is added and is 3 ~ 30% Solution is as peptizing agent, and drying condition is in 80 ~ 120 DEG C of dry 1 ~ 5h, and roasting condition is that 1 ~ 5h is roasted at 400 ~ 500 DEG C.

8. according to the method described in claim 1, it is characterized in that：Step（2）Or step（5）Described in active metal be member The VIIIth race in plain periodic table and/or the VIth race's metallic element.

9. according to the method described in claim 8, it is characterized in that：VIIIth race's active metal is Ni, the VIth race activity gold It is W and/or Mo to belong to.

10. according to the method described in claim 1, it is characterized in that：Step（3）The alkene be carbon atom number 2 ~ 10 just The alkene of structure or isomery, alkadienes.

11. according to the method described in claim 1, it is characterized in that：Step（3）The alkene is hexadiene, nhepene.

12. according to the method described in claim 1, it is characterized in that：Step（4）By step（3）The carbon deposition catalyst of preparation carries Body is directly added into the advance Muffle kiln roasting for being warming up to 450 ~ 550 DEG C 20 ~ 150 minutes, burn off catalyst carrier surface layer carbon distribution, So that carrier inside carbon deposition quantity accounts for step（3）The 40 ~ 80% of total carbon deposition quantity.