CN105709801B

CN105709801B - A kind of preparation method of chemical industry type hydrocracking catalyst

Info

Publication number: CN105709801B
Application number: CN201410723844.9A
Authority: CN
Inventors: 柳伟; 杜艳泽; 王凤来; 刘昶; 秦波; 张晓萍
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2014-12-04
Filing date: 2014-12-04
Publication date: 2018-01-16
Anticipated expiration: 2034-12-04
Also published as: CN105709801A

Abstract

The present invention discloses a kind of preparation method of hydrocracking catalyst, including following content：（1）Prepare carrier of hydrocracking catalyst；（2）Saturation impregnation steps（1）The carrier of hydrocracking catalyst of preparation, then it is dried, is calcined；（3）With liquefied olefines saturation impregnation steps（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 top layer carbon distribution；（5）Prepare Mo Ni or W Ni active metal salt solutions, saturation impregnation steps（4）Carrier after roasting, hydrocracking catalyst finished product is obtained after drying, roasting.Hydrocracking catalyst prepared by this method can carry out selective hydrogenation to crackate heavy naphtha and tail oil, both reduce the hydrogen consumption of device, can also produce the heavy naphtha and tail oil product of high quality simultaneously.

Description

A kind of preparation method of chemical industry type hydrocracking catalyst

Technical field

The present invention relates to a kind of preparation method of hydrocracking catalyst, relates in particular to a kind of chemical industry type and is hydrocracked The preparation method of catalyst.

Background technology

As crude quality becomes weight, variation year by year, environmental regulation is increasingly strict, and market is continuous to the demand of clear gusoline Increase so that the hydrogen addition technology for producing clean fuel obtains more and more extensive application.In the secondary operation technology of crude oil, evaporate Point oily hydrocracking technology has the characteristics that strong adaptability to raw material, production operation and products scheme flexibility is big, 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 in full factory's production procedure and product quality is adjusted The effect of device is saved, 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 first 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.Cut Only 2012, the global total working ability of hydrocracking unit reached more than 2.78Mt/a, accounts for crude oil time processing ability 6.26%。

China is one of 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.Into 21 century, with rapid development of economy, oil production The demand rapid growth of product, CNPC's 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, far above world average level.But hydrocracking technology application market development in China's is weighed with skewness, place 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 ethene 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 is in itself and petroleum product-quality requires increasingly strict, 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 hydrogenation is split Change technical merit and propose higher requirement.

The core of hydrocracking technology is hydrocracking catalyst, and the technology of its technology depends on carrying for catalyst performance Rise.Hydrocracking catalyst is bifunctional catalyst, comprising adding dehydrogenation functionality and cracking function.Usual cracking function is carried by acidity Body component provides, and mainly includes molecular sieve and amorphous oxide.And add dehydrogenation functionality mainly to be provided by hydrogenation metal, hydrogenation gold 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 infusion process of non-noble metal components etc. in agent, wherein with dipping Method is the most commonly used, accounts for existing commercial Application hydrocracking catalyst more than 80%.Infusion process prepares hydrocracking catalyst, system Standby range request hydrogenation metal salt of crossing can make the metal salt solution that stability is good, concentration is high.Hydrocracking catalyst category In fine chemical product, preparation technology 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 frequently used metal promoter component of hydrocracking catalyst.In order to ensure The materialization of hydrocracking catalyst and catalytic performance, the metallic salt for requiring to introduce in its preparation process remove after Roasting Decomposition Outside oxygen element, remained without other elements.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 for preparing high-activity hydrocracking catalyst, is helped by ammonium metatungstate, nickel nitrate one kind Preserved material, obtained with carrier prepared catalyst performance of the co-impregnated solution dipping containing Y type molecular sieve, refractory inorganic oxides bright Aobvious lifting.Patent CN88103069.4 gives a kind of preparation method of supported non-noble metal hydrocracking catalyst, its 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 keeps gas in constant, product to generate when the catalyst of preparation has reaction temperature rise Amount less, coking situation be similar to using conventional molecular sieve as acidic components catalyst the characteristics of, suitable for mild hydrocracking.Patent US5,229,347 give a kind of preparation method of hydrocracking catalyst, and this prepares catalyst and includes VIB and VIII groups Metal component is closed, after catalyst carrier shaping, metal component is introduced using infusion process, dipping rear catalyst is by drying, 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. Feature, various heavy inferiors can be fed to high-quality jet fuel, diesel oil, the lube basestocks for being converted into market in urgent need 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 hydrogenation two Process, cracking on the one hand is carried out to heavy raw oil and is converted into light fraction oil ingredient, is on the other hand carried out while cracking Hydrogenation, 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 put, its product is mainly heavy naphtha and tail oil, respectively as the reaction of reformer and ethylene unit Charging.The requirement that hydrocracking process is hydrogenated with for heavy naphtha and tail oil is different, and the heavy naphtha of cracking generation adds The virtue that hydrogen can reduce heavy naphtha is dived, and this is unfavorable for reformer.And as feed ethylene tail oil part hydrogenation then The arene content in tail oil is advantageously reduced, is advantageous to improve ethylene unit yield and service cycle, and existing is hydrocracked Catalyst does not solve the above problems well.

The content of the invention

In view of the shortcomings 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, the heavy naphtha and tail oil product of high quality can also be produced 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, add acid Property peptizing agent, through being molded, dry and roasting, prepare carrier of hydrocracking catalyst；

（2）Prepare and content is counted as 10 ~ 30g/100ml using oxide, preferably 17 ~ 28g/100ml Mo-Co active metal salts Solution, saturation impregnation steps（1）The carrier of hydrocracking catalyst of preparation, then it is dried, is calcined；

（3）With liquefied olefines saturation impregnation steps（2）Catalyst after the roasting of acquisition, 50 ~ 400 DEG C add 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 top layer carbon distribution so that carrier inside carbon deposition quantity account for total carbon deposition quantity before roasting 10% ~ 90%；

（5）Prepare and content is counted as 40 ~ 80g/100ml using oxide, preferably 45 ~ 60g/100ml Mo-Ni or W-Ni activity Metal salt solution, saturation impregnation steps（4）Carrier after roasting, hydrocracking catalyst finished product is obtained after drying, roasting.

The inventive method 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 the one or more in 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 also include inorganic refractory oxide, generally aluminum oxide or aluminum oxide containing auxiliary agent, use When typically using aluminum hydroxide solid elastomer powder as raw material.There is macropore in amorphous preferred this area of acidic components and aluminum oxide Hold, the raw material of bigger serface.

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

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

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

The inventive method step（5）Described hydrogenation catalyst finished product, specific surface area are 200 ~ 400m²/ g, pore volume 0.2 ~ 0.5ml/g, 30 ~ 90wt% containing acid material in carrier, preferably 40 ~ 70wt%, surplus are aluminum 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 inventive method can improve the matter of heavy naphtha and hydrocracking tail oil simultaneously Amount, hydrogen consumption is reduced, is a kind of excellent chemical industry type hydrocracking catalyst.

Embodiment

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

Embodiment 1

（1）Take butt weight 150g Y molecular sieve and butt weight 250g macroporous aluminium oxide it is well mixed after, add 3g/100ml dust technologies 200ml is rolled, extruded moulding, then, through 120 DEG C of dry 4h, is obtained carrier after 550 DEG C of roasting 3h, is compiled Number it is T-1；（2）Configure Mo-Co maceration extracts：Ammonium molybdate 241g and cobalt nitrate 240g is taken to configure 1000ml dippings after being dissolved in water molten Liquid, active metal is with MoO in gained dipping solution₃It is respectively 20g/100ml and 6g/100ml with CoO cubages, numbering is RY-1；Take T-1 300g to impregnate 2h in 600ml RY-1, then, take out carrier normal 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, numbering CTL-1；（3）Take CTL-1 300g to be positioned in 600ml hexadiene solvents to soak Stain 4h, then, it is directly placed into and is previously heated in 450 DEG C of Muffle furnace after 150 DEG C of heating abundant carbon distributions of 15h in air atmosphere Roasting obtains CTL-2 for 30 minutes, 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：Ammonium metatungstate 482g and nickel nitrate 480g is taken to configure 1000ml dipping solutions, gained dipping after being dissolved in water Active metal is with WO in solution₃It is respectively 40g/100ml and 12g/100ml with NiO cubages, numbering RY-2；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 O₃、MoO₃, CoO and NiO contents be respectively 9%, 14%, 3% and 4%, evaluation procedure and result are listed in 1 ~ table of table 3

Embodiment 2

（1）Take butt weight 200g Y molecular sieve and butt weight 200g macroporous aluminium oxide it is well mixed after, add 3g/100ml dust technologies 200ml is rolled, extruded moulding, then, through 120 DEG C of dry 4h, is obtained carrier after 550 DEG C of roasting 3h, is compiled Number it is T-2；（2）Configure Mo-Co maceration extracts：Ammonium molybdate 241g and cobalt nitrate 240g is taken to configure 1000ml dippings after being dissolved in water molten Liquid, active metal is with MoO in gained dipping solution₃It is respectively 18g/100ml and 5g/100ml with CoO cubages；Take T-2 300g impregnates 2h in 600ml RY-3, then, takes out carrier normal temperature and dries in the air 100 DEG C of drys 4h after 2h processed, 500 DEG C of roasting 3h acquisitions Low-metal content carrier, numbering CTL-3；（3）Take CTL-3 300g to be positioned in 600ml nhepene solvents and impregnate 4h, then, It is directly placed into after the lower 200 DEG C of heating abundant carbon distributions of 20h of air atmosphere and is previously heated to 500 DEG C of Muffle kiln roasting 40 minutes, CTL-4 is obtained, CTL-4 carrier insides carbon deposition quantity is 50% of total carbon deposition quantity before its roasting；（4）It is molten to configure high concentration W-Ni dippings Liquid：Ammonium metatungstate 482g and nickel nitrate 480g is taken to configure 1000ml dipping solutions after being dissolved in water, activity in gained dipping solution Metal is with WO₃It is respectively 36g/100ml and 12g/100ml with NiO cubages, numbering RY-4；300gCTL-4 is satisfied And dipping, then, final catalyst CT-2 is obtained after 100 DEG C of dry 4h, 500 DEG C of roasting 4h.Active metal MoO in CT-2₃、 NiO and CoO contents are respectively 23%, 4% and 3%, and 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 control WO₃Contain with NiO Amount is respectively 35g/100ml and 10g/100ml, after supersaturation impregnates 2h, is dried, roasting obtains comparative example catalyst, numbering The upper active metal W O of BCT-1, BCT-1₃、MoO₃, CoO and NiO contents be respectively 9%, 14%, 3% and 4%, evaluation result be listed in table 1 ~ Table 3.

Comparative example 2

Without step（3）Hexadiene impregnation process, remaining prepares active metal in sample CT-2 with embodiment 1 MoO₃, NiO and CoO contents be respectively 23%, 4% and 3%, evaluation procedure and result are listed in 1 ~ table of table 3.

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 the method for comparative example 1 ~ 2 Agent, evaluation result are listed in 1 ~ table of table 3.

The raw material oil nature of table 1

The embodiment 1 ~ 2 of table 2 and comparative example 1 ~ 2 use operating condition

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

Show by using contrast test of the embodiment 1 with the catalyst of comparative example 1 on evaluating apparatus, using present invention side 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.Sent out by embodiment 2 and the contrast of comparative example 2 Catalysis existing, that catalyst prepared by the inventive method was once incrementally distributed from inside to outside with the active metal conventionally prepared Agent is compared, and shows more preferable effect, and its scheelite virtue is latent higher, and chemical hydrogen consumption is lower, the obvious reduction of BMCI values, 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 Agent diffusion inside is relevant, and the uneven distribution of catalyst activity metal can be preferably formed using the inventive method, therefore, Show more preferable reactivity worth.In addition, Mo-Ni, W-Ni active metal of the high hydrogenation activity of the inventive method are lived with low hydrogenation Property Mo-Co active metals on a catalyst support reasonably matching be distributed with beneficial to play different activities metal the characteristics of, urge Agent selective hydrogenation ability is stronger.

Claims

A kind of 1. 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, add Aci-Jel Solvent, through being molded, dry and be calcined, prepare carrier of hydrocracking catalyst；

（2）Prepare and Mo-Co active metal salt solution of the content as 10 ~ 30g/100ml, saturation impregnation steps are counted using oxide（1） The carrier of hydrocracking catalyst of preparation, then it is dried, is calcined；

（3）With liquefied olefines saturation impregnation steps（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 top layer carbon distribution so that carrier inside carbon deposition quantity accounts for 10% ~ 90% of total carbon deposition quantity before roasting；

（5）Prepare and Mo-Ni or W-Ni active metal salt solution of the content as 40 ~ 80g/100ml, saturation dipping step are counted using oxide Suddenly（4）Carrier after roasting, hydrocracking catalyst finished product is obtained after drying, roasting.
2. according to the method for claim 1, it is characterised in that：Step（1）Described in acid cracking material include molecule Sieve and amorphous acidic components.
3. according to the method for claim 2, it is characterised in that：Molecular sieve includes Y type molecular sieve, beta-molecular sieve, ZSM-5 point One or more in sub- sieve, SAPO molecular sieve, MCM-41 molecular sieves.
4. according to the method for claim 2, it is characterised in that：Amorphous acidic components are amorphous silica-alumina, amorphous silicon One or more in magnesium, clay.
5. according to the method for claim 1, it is characterised in that：Step（1）In acid cracking material be Y type molecular sieve.
6. according to the method for claim 1, it is characterised in that：Step（1）Described in carrier of hydrocracking catalyst material Material includes inorganic refractory oxide, is aluminum oxide or aluminum oxide containing auxiliary agent, uses using aluminum hydroxide solid elastomer powder as raw material.
7. according to the method for claim 1, it is characterised in that：Step（1）It is middle to add the nitric acid aqueous solution that mass fraction 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 calcined at 400 ~ 500 DEG C.
8. according to the method for claim 1, it is characterised in that：Step（2）Middle preparation counts content as 17 ~ 28g/ using oxide 100ml Mo-Co active metal salt solutions.
9. according to the method for claim 1, it is characterised in that：Step（3）Described alkene be carbon number 2 ~ 10 just The alkene of structure or isomery, alkadienes.
10. according to the method for claim 1, it is characterised in that：Step（3）Described alkene is hexadiene, nhepene.
11. according to the method for claim 1, it is characterised in that：Step（4）By step（3）The carbon deposition catalyst of preparation carries Body is directly added into be warming up in 450 ~ 550 DEG C of Muffle furnace 20 ~ 150 minutes in advance, burn off catalyst carrier top layer carbon distribution so that Carrier inside carbon deposition quantity account for roasting before carbon deposition quantity 40 ~ 80%.
12. according to the method for claim 1, it is characterised in that：Step（5）Prepare and content is counted as 45 ~ 60g/ using oxide 100ml Mo-Ni or W-Ni active metal salt solutions.