CN105642336B

CN105642336B - A kind of technology of preparation method of hydrocracking catalyst

Info

Publication number: CN105642336B
Application number: CN201410723838.3A
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: 2018-04-10
Anticipated expiration: 2034-12-04
Also published as: CN105642336A

Abstract

The present invention discloses a kind of technology of preparation method of hydrocracking catalyst, including following content：（1）Prepare carrier of hydrocracking catalyst；（2）Prepare salting liquid, saturation impregnation steps（1）The carrier of hydrocracking catalyst of preparation, then it is dried, is calcined；（3）Step（2）Carrier carries out unsaturation with organic solvent not soluble in water and sprayed after the roasting of acquisition；（4）Step（3）Carrier after unsaturation dipping organic solvent handles 0.5 3h in the case where pressure is 0.5~10.0MPa indifferent gas atmosphere；（5）Prepare salting liquid, saturation impregnation steps（4）Obtained carrier, 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 technology of preparation method of hydrocracking catalyst

Technical field

The present invention relates to a kind of technology of preparation method of hydrocracking catalyst, relates in particular to a kind of chemical industry type hydrogenation The technology of preparation method of Cracking 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 technology 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 active metallic content counted as 10 ~ 30g/100ml using oxide, preferably 17 ~ 28g/100ml salting liquid, Saturation impregnation steps（1）The carrier of hydrocracking catalyst of preparation, then it is dried, is calcined；

（3）Step（2）Carrier carries out unsaturation with organic solvent not soluble in water and sprayed after the roasting of acquisition, wherein impregnating The volume of liquid is the 30 ~ 80% of carrier saturated water adsorptive value, preferably 50-70%；

（4）Step（3）Carrier after unsaturation dipping organic solvent is in the indifferent gas atmosphere that pressure is 0.5~10.0MPa Lower processing 0.5-3h；

（5）Prepare and active metallic content counted as 40 ~ 80g/100ml using oxide, preferably 45 ~ 60g/100ml salting liquid, Saturation impregnation steps（4）Obtained carrier, 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（2）Or step（4）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 inventive method step（3）Described organic solvent not soluble in water include alkane, petroleum ether, carbon tetrachloride, One or more in benzene, toluene, ethylbenzene, dimethylbenzene, anthracene, naphthalene, phenanthrene, preferably one kind or several in normal heptane, petroleum ether, toluene Kind, further preferred normal heptane.

The inventive method step（4）Carrier after unsaturation dipping organic solvent is in the inert atmosphere that pressure is 3~5MPa Enclose lower processing 1-2h.

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 active component prepared by the inventive method is in uneven distribution, can improve scheelite brain simultaneously The quality of oil and hydrocracking tail oil, 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 W-Ni maceration extracts：Ammonium metatungstate 241g and nickel nitrate 240g is taken to configure 1000ml dippings after being dissolved in water Solution, active metal is with WO in gained dipping solution₃It is respectively 20g/100ml and 6g/100ml with NiO 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）Using the method sprayed, 210ml normal heptane solvents pair are taken 300g CTL-1 are sprayed, and then, are placed in 2h in 3.0MPa nitrogen atmospheres, obtain CTL-2, the volume of normal heptane in the carrier Content is the 70% of carrier total pore volume；（4）Configure high concentration W-Ni dipping solutions：Ammonium metatungstate 482g and nickel nitrate 480g is taken to add 1000ml dipping solutions are configured after water dissolving, active metal is with WO in gained dipping solution₃It is respectively 40g/ with NiO cubages 100ml and 12g/100ml, numbering RY-2；The method sprayed using saturation, is sprayed to 300gCTL-2, then, 100 DEG C 3h is dried, final catalyst CT-1 is obtained after 500 DEG C of roasting 3h.Active metal W O in CT-1₃It is respectively 24% He with NiO contents 7%, evaluation procedure is listed in 1 ~ table of table 3 with result

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 W-Ni maceration extracts：Ammonium metatungstate 241g and nickel nitrate 240g is taken to configure 1000ml dippings after being dissolved in water Solution, active metal is with WO in gained dipping solution₃It is respectively 20g/100ml and 6g/100ml with NiO cubages, numbering is RY-3；Take T-2 300g to impregnate 2h in 600ml RY-3, 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-3；（3）Using the method sprayed, 150ml petroleum ether solvents pair are taken 300g CTL-3 are sprayed, and then, are placed in 1h in 5.0MPa nitrogen atmospheres, obtain CTL-4, the volume of petroleum ether in the carrier Content is the 50% of carrier total pore volume；（4）Configure high concentration W-Ni dipping solutions：Ammonium metatungstate 482g and nickel nitrate 480g is taken to add 1000ml dipping solutions are configured after water dissolving, active metal is with WO in gained dipping solution₃It is respectively 36g/ with NiO cubages 100ml and 12g/100ml, numbering RY-4；The method sprayed using saturation, is sprayed to 300gCTL-4, then, 100 DEG C 4h is dried, final catalyst CT-2 is obtained after 500 DEG C of roasting 4h.Active metal W O in CT-2₃It is respectively 23% He with NiO contents 7.2%, evaluation procedure is listed in 1 ~ table of table 3 with result.

Embodiment 3

（1）Take butt weight 250g Y molecular sieve and butt weight 150g 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-3；（2）Configure W-Ni maceration extracts：Ammonium metatungstate 180g and nickel nitrate 160g is taken to configure 1000ml dippings after being dissolved in water Solution, active metal is with WO in gained dipping solution₃It is respectively 15g/100ml and 4g/100ml with NiO cubages, numbering is RY-5；Take T-3 300g to impregnate 2h in 600ml RY-5, 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-5；（3）Using the method sprayed, 150ml toluene solvants are taken to 300g CTL-5 is sprayed, and then, is placed in 2h in 3.0MPa nitrogen atmospheres, obtains CTL-6, and the volume content of toluene in the carrier is The 50% of carrier total pore volume；（4）Configure high concentration W-Ni dipping solutions：Ammonium metatungstate 482g and nickel nitrate 480g is taken to be dissolved in water 1000ml dipping solutions are configured afterwards, and active metal is with WO in gained dipping solution₃It is respectively 45g/100ml with NiO cubages And 15g/100ml, numbering RY-6；The method sprayed using saturation, is sprayed to 300gCTL-6, then, 100 DEG C of dryings Final catalyst CT-3 is obtained after 4h, 500 DEG C of roasting 4h.Active metal W O in CT-3₃It is respectively 21.4% He with NiO contents 6.4%, 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-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）, remaining is listed in 1 ~ table of table 3 with embodiment 2, evaluation procedure with result.

Comparative example 3

Without step（3）In be placed in 2h processes in 3.0MPa nitrogen atmospheres, remaining is the same as embodiment 3, evaluation procedure and result It is listed in 1 ~ table of table 3

The reactivity worth of catalyst is prepared with comparative example 1 ~ 3 in order to investigate embodiment 1 ~ 3, 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 ~ 3 and the method for comparative example 1 ~ 3 Agent.

The raw material oil nature of table 1

The embodiment 1 ~ 3 of table 2 and comparative example 1 ~ 3 use operating condition

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

Show by using the contrast test of embodiment, comparative example catalyst on evaluating apparatus, using the inventive method The catalyst of preparation is compared with the equally distributed hydrocracking catalyst of active metal prepared using conventional method, tail oil 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, and BMCI values are lower, and this is adopted with the present invention It is relevant that organic solvent blocks high concentration active metal maceration extract double-steeping process to be spread to catalytic inner, using this hair Bright method can preferably form the uneven distribution of catalyst activity metal, therefore, show more preferable reactivity worth.

Claims

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

（2）Prepare and salting liquid of the active metallic content as 10 ~ 30g/100ml, saturation impregnation steps are counted using oxide（1）Prepare Carrier of hydrocracking catalyst, then it is dried, is calcined；

（3）Step（2）After the roasting of acquisition carrier carries out unsaturation with organic solvent not soluble in water and sprayed, wherein maceration extract Volume is the 30 ~ 80% of carrier saturated water adsorptive value；

（4）Step（3）Carrier after unsaturation dipping organic solvent is located in the case where pressure is 0.5~10.0MPa indifferent gas atmosphere Manage 0.5-3h；

（5）Prepare and salting liquid of the active metallic content as 40 ~ 80g/100ml, saturation impregnation steps are counted using oxide（4）Obtain Carrier, 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）Described in carrier of hydrocracking catalyst material Material also includes inorganic refractory oxide.

6. according to the method for claim 5, it is characterised in that：Inorganic refractory oxide is aluminum oxide or aoxidized containing auxiliary agent Aluminium, using aluminum hydroxide solid elastomer powder as raw material during use.

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.

8. according to the method for claim 1, it is characterised in that：Drying condition is in 80 ~ 120 DEG C of dry 1 ~ 5h, is calcined bar Part is that 1 ~ 5h is calcined at 400 ~ 500 DEG C.

9. according to the method for claim 1, it is characterised in that：Step（2）Described in active metal be the periodic table of elements In the VIIIth race and/or the VIth race's metallic element.

10. according to the method for claim 9, it is characterised in that：VIIIth race's active metallic element is Ni, from alkali Formula nickelous carbonate, nickel nitrate or nickel acetate, the VIth race's active metallic element are W and/or Mo, from ammonium metatungstate, ammonium molybdate or Molybdenum trioxide.

11. according to the method for claim 1, it is characterised in that：Step（3）Described organic solvent not soluble in water includes One or more in alkane, petroleum ether, carbon tetrachloride, benzene, toluene, ethylbenzene, dimethylbenzene, anthracene, naphthalene, phenanthrene.

12. according to the method for claim 11, it is characterised in that：Step（3）Described organic solvent bag not soluble in water Include the one or more in normal heptane, petroleum ether, toluene.

13. according to the method for claim 1, it is characterised in that：Step（5）Described hydrocracking catalyst finished product, than Surface area is 200 ~ 400m²/ g, pore volume are 0.2 ~ 0.5ml/g, and acid cracking 30 ~ 90wt% of material is contained in carrier, and surplus is oxidation Aluminium, the mass content of carrier and active metal is respectively 55 ~ 85% and 15 ~ 45% in catalyst, and the VIIIth race's active metal quality contains Measure as 3 ~ 15%.