CN104646048B - A kind of preparation method of hydrogenation catalyst - Google Patents
A kind of preparation method of hydrogenation catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of hydrogenation catalyst, including：（1）Prepare catalyst carrier；（2）Prepare metal compound solution containing hydrogenation active component, by hydrogenation active component group vib and VIII metallic compounds one or more, using ammonium salt or acidic oxide, VIII metallic compounds use soluble halide to wherein vib metal compound；（3）Using step（2）Preparing metal compound solution impregnation steps（1）Carrier, the material after dipping is dried, then carry out property adjustment, finally dry, roasting obtain catalyst prod.The inventive method can solve the problems, such as difficult pollutant emission in hydrogenation catalyst production process, and the performance of catalyst is further improved.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogenation catalyst, especially the hydrogenation without NOx emission is urged in preparation process
The preparation method of agent.
Technical background
Hydrogen addition technology particularly hydrocracking technology, with adaptability to raw material is strong, production operation and products scheme flexibility
Greatly, the features such as good product quality, the charging of various heavy inferiors can be converted into high-quality jet fuel, the bavin of market in urgent need
Oil, lube basestocks and chemical industry naphtha and tail oil preparing ethylene by steam cracking raw material, it has also become modern times oil refining and oil
One of industrial most important heavy oil deep processing technique is learned, increasingly extensive application is at home and abroad obtained.Hydrocracking technology
Key is hydrocracking catalyst, and the raising of its level depends on the exploitation of high-performance catalyst for hydrocracking.Foreign countries' hydrogenation splits
Changing catalyst development patent business mainly has CLG companies, Uop Inc., Criterion catalyst Co.s, Haldor Topsoe public
Department, Albemarle companies and Axens companies etc..China is the country for grasping distillate hydrocracking technology earliest in the world
One.With the sustainable development of national economy, hydrocracking unit working ability is improved constantly, and existing disposal ability is alreadyd exceed
50.0Mt/a.By the long-term and unremitting effort of domestic several generations hydrogenation scientific and technical personnel, A wide selection of colours and designs, series matching are developed
Hydrocracking catalyst and technology, and be industrially widely applied, China's oil refining and chemical industry are met very well
The need for industrial development.
The geometric shape and physical dimension of catalyst, to fluid resistance, air velocity, the distribution of bed temperature gradient, concentration
Gradient distribution etc. all has an impact.In order to give full play to its catalysis potentiality, optimal profile and size should be selected, this is accomplished by
Select most suitable forming method.The forming method of hydrocracking catalyst mainly has template, compressing tablet, spin, oil ammonia column balling-up
With extrusion etc., wherein extruded moulding technology is most widely used.Need to add a certain amount of adhesive during extruded moulding
Or diluted acid peptizing agent, effect is to play cementation, it is ensured that shaping rear catalyst has certain geometry appearance shape and higher
Pressure-resistant, wear-resisting intensity.The preparation of adhesive is mainly and is uniformly mixed according to a certain percentage with alumina dry glue by diluted acid, is passed through
Stirring, ageing obtain jelly.Because nitric acid is low with acid strong, easily decomposition, price, and in the catalyst without residual after decomposition
The advantages of staying, is to prepare the most-often used sour peptizing agent of hydrocracking catalyst.Such as CN00110016.5 and
CN00123221.5 describes two kinds of oil refining class loaded catalyst extruded moulding methods and selects nitric acid as Aci-Jel respectively
Solvent, and US7,687,676 Ludox for directly using nitric acid to be acidified or Alumina gel as shaping of catalyst during it is viscous
Mixture.
Hydrocracking catalyst preparation method is varied, wherein most importantly infusion process, coprecipitation method, kneading method and from
Sub- exchange process etc., these preparation methods are in hydrogenation catalyst production field extensive use.Wherein infusion process is widely used in hydrogenation
The preparation of Cracking catalyst.Infusion process prepares hydrocracking catalyst, and preparation process requirement hydrogenation metal salt can make
Good stability, concentration metal salt solution high.Hydrocracking catalyst belongs to fine chemical product, and preparation technology is complicated, production
Process is restricted by many factors.The hydrogenation activity of hydrocracking catalyst is in VI B races and VIII race in the periodic table of elements
Metal component, most widely used is tetra- kinds of elements of W, Mo, Ni, Co.Wherein nickel（Or cobalt）It is the most frequently used hydrocracking catalyst
Metal promoter component.In order to ensure materialization and the catalytic performance of hydrocracking catalyst, require to introduce in its preparation process
Metallic salt after Roasting Decomposition in addition to oxygen element, without other elements residual.It is hydrogenated with when being prepared using infusion process and coprecipitation method
During Cracking catalyst, in addition it is also necessary to configure that concentration is high, good stability metal compound solution.Nickel metal（Or cobalt）Chemical combination
In thing, nitrate has the advantages that solubility is high, stability of solution is good, decompose after noresidue, prepared in hydrocracking catalyst
During be widely used.CN96109702.7 provides a kind of co-impregnated solution for preparing high-activity hydrocracking catalyst, by inclined tungsten
A kind of leaching agent of sour ammonium, nickel nitrate, is impregnated containing prepared by Y type molecular sieve, the carrier of refractory inorganic oxides with the co-impregnated solution
Catalyst performance is obviously improved.
CN97121663.0 gives a kind of beta-zeolite molecular sieve catalyst and preparation method thereof, in the preparation of catalyst
The aluminum oxide precursor thing of nitric acid and small pore volume is used in journey（Boehmite）The adhesive of preparation carries out extruded moulding, in metal
The method that adding procedure is then impregnated using the nitrate of group VIII metal element, although obtained on catalyst strength with reactivity worth
Obtain preferable effect.But hydrocracking catalyst patent described above, in hydrocracking catalyst shaping and hydrogenation metal addition
During, it is required to largely use nitric acid and nickel nitrate, these nitrate ions to be thermally decomposed in roasting process, discharge big
The NOx of amount, causes suitable harm, is to restrict one of key factor that hydrocracking catalyst is produced.NOx is a kind of important big
Gas environmental contaminants, are to form acid rain, photochemical fog and cause one of primary pollution source of ozone hole.In addition, big
Measuring the generation of NOx also can cause heavy corrosion to production equipment and greatly infringement is caused to operator's health.According to statistics, often give birth to
Producing 1 ton of hydrocracking catalyst will produce about 45 standard cubic meter NOx.Nearly ten thousand tons of whole world hydrocracking catalyst annual production,
And the hydrotreating and hydrofinishing class catalyst whole world annual production similar to hydrocracking catalyst is even more surprising, its production
The pollution that process is caused to atmospheric environment, has received more and more attention.
With increasingly strict, the NO in solution catalyst preparation process of environmental lawxPollution problem increasingly receives pass
Note.For cleaning for catalyst production process, people have selected some cleanings to be discharged without ammonia nitrogen in catalyst preparation process
Raw material.In hydrocracking catalyst preparation process, selection can meet catalyst preparation process and physical and chemical performance requirement
Cleaning acids as peptizing agent, and without NOx produce metallic salt as nitrate substitute, be realize be hydrocracked
The key problem in technology for cleaning of catalyst preparation process.CN00110016.5 and CN00123221.5 describe two kinds of oil refining respectively
Class loaded catalyst extruded moulding method.In the selection of Aci-Jel solvent, except nitric acid can be used as peptized acidic
Agent, two schemes employ the selection of more inorganic and organic acids, such as inorganic acid can select phosphoric acid, hydrochloric acid, sulfuric acid or
The combination of several acid, organic acid can be with formic acid, acetic acid, oxalic acid, citric acid etc..But after these inorganic acids are thermally decomposed
The impurities lefts such as Cl, S, P are there is, the peptizing agent of shaping of catalyst is not suitable as；And organic acid is then because its acid
The weaker satisfaction that is difficult to of property prepares high mechanical properties requirement catalyst or carrier.CN201010211884.7 is then given using water-soluble
Property the metallic solution that is impregnated as hydrocracking catalyst of metal mixed solution prepared of organic acid nickel salt, the catalysis prepared
Agent has obvious catalyzed conversion ability to heavy aromatics, and these organic nickel salts can be nickel acetate, nickel formate, citric acid nickel, second
Diacid nickel etc., substitutes nickel nitrate, it is possible to achieve the life of the cleaning of hydrocracking catalyst metal adding procedure using organic nickel salt
Produce.However, according to《Handbook of inorganic chemistry》Data of inquiry, and simulate patent experiment, the solubility of organic nickel salt compared with
Low, 25 DEG C of solubility in water of such as four water acetic acid nickel is only the water acetic acid nickel of 16.0g tetra-/100mL（4.9gNiO/100mL）,
It is difficult to make the metal salt solution of high-concentration stable, it is difficult to meet the requirement that conventional impregnation method prepares hydrocracking catalyst.
And some other inorganic acid VIII salt, although with solubility higher, such as the group VIII metal salt of halogen family, sulfuric acid
Class, but group VIII metal halogen family salt is stronger with the active force of carrier, and the Hydrogenation of catalyst is affected.
The content of the invention
There is solubility higher for halogen family strong acid group VIII metal salt, roasting process can meet without NOx emission
Cleaning prepares catalyst requirement, but increased the active force between active metal component and carrier, reduces Hydrogenation, this hair
Bright solution solves the problem by post-processing approach, improves the performance of catalyst, and realize the clear of hydrogenation catalyst
Clean preparation.
Hydrogenation catalyst preparation method process of the present invention includes following content：
（1）Prepare catalyst carrier；
（2）Metal compound solution containing hydrogenation active component is prepared, by hydrogenation active component group vib and VIII metal compounds
One or more of thing, group vib metallic compound is selected from least one in W and Mo compounds, and VIII metallic compounds are selected from
At least one in Ni and Co compounds；Wherein vib metal compound uses ammonium salt or acidic oxide, VIII metallic compounds
Using soluble halide；
（3）Using step（2）Preparing metal compound solution impregnation steps（1）Carrier, the material after dipping is carried out
Dry, impregnation process is then carried out using ammoniacal liquor, sal volatile or ammonium bicarbonate soln, finally dry, roasting is catalyzed
Agent product.
In the present invention, step（1）The preparation of catalyst carrier can use this area conventional method, according to catalyst performance
The requirement selection carrier material of matter, by preparation process such as mixing, shaping, dry and roastings, obtains catalyst carrier.For adding
For hydrogen Cracking catalyst, carrier material at least includes a kind of acidic cracking components；Carrier of hydrocracking catalyst is prepared, by acid
Property carrier component such as modified molecular screen, macroporous aluminium oxide powder and/or contained amorphous silica-alumina dry glue powder, and other extrusion aids, such as
The mixtures such as expanding agent, lubricant carry out it is fully dry-mixed after, add organic acid or halogen family strong acid adhesive to be molded, extrusion,
Banded extruder orifice plate can be cylinder, clover, bunge bedstraw herb or other abnormal shapes, then carry out low temperature drying, and high-temperature roasting is activated,
Prepare the carrier of hydrocracking catalyst of high intensity.
Acid cracking material of the present invention includes molecular sieve or amorphous acidic components, and molecular sieve generally comprises Y types
One or more, amorphous in molecular sieve, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieves etc.
Acidic components are generally one or more in amorphous silica-alumina, amorphous silicon magnesium and clay etc..Required molecular sieve can be with root
Suitable being modified is carried out according to performance requirement.Carrier material can also include acid weaker inorganic in hydrocracking catalyst
Refractory oxide, generally aluminum oxide or aluminum oxide containing auxiliary agent are general with aluminum hydroxide solid elastomer powder as raw material when using.Without fixed
The raw material with big pore volume, bigger serface in the preferably this area such as shape acidic components and aluminum oxide.By in final catalyst
Weight content meter, the acid cracking general content of material is 1% ~ 60%, preferably 5%~40%, and hydrogenation active component is in terms of oxide
Weight content in the catalyst is generally 15% ~ 50%, preferably 20% ~ 40%, while can be with salic less than 50%.
Step（1）Middle peptizing agent is generally acid solution, such as formic acid, acetic acid, ethanedioic acid, citric acid organic acid and/or
One kind or mixed acid of phosphoric acid, it would however also be possible to employ inorganic halogen family strong acid, binding agent is generally by the small porous aluminum oxide of peptization.Into
Type can determine according to the shape of final catalyst, such as cylinder, clover, bunge bedstraw herb, irregular strip.The roasting of catalyst carrier
Temperature is generally 300 ~ 600 DEG C, and roasting time is generally 2 ~ 10 hours.
Step（2）In the metal compound solution containing hydrogenation active component in, group vib metallic compound can be selected from molybdenum
In acid, para-molybdic acid, molybdate, paramolybdate, wolframic acid, metatungstic acid, ethyl metatungstic acid, tungstates and metatungstate at least one
Kind, wherein it is preferred that ammonium paramolybdate and/or metatungstic acid ammonium salt.Group VIII metal species is mainly nickel and/or cobalt, and it has inorganic acid
Salt can be chloride or bromide etc., preferably chloride.
Step（2）In can be added as needed on suitable adjuvant component, such as in dipping solution contain P, F, B, Zr, Ti
In the compound of one or more.
Step（3）Ammoniacal liquor, sal volatile or ammonium bicarbonate soln spray processing procedure, and the concentration of solution is generally
0.5~6mol/L, preferably 1~4mol/L.Solution usage is generally the 30%~200% of material water absorption rate, preferably 50%~
100%.Step（3）In drying and roasting can use normal condition, dry that general that 2~48 are dried at 50~200 DEG C is small
When, roasting is general to be calcined 2~10 hours at 300~600 DEG C.
Hydrogenation catalyst prepared by the inventive method has following property, and specific surface area is 120m2/g ~450m2/ g, preferably
It is 160m2/g~400m2/g；Pore volume is 0.20cm3/g~0.50cm3/ g, preferably 0.30cm3/g ~0.45cm3/ g, hydrogenation metal
Total content is 15% ~ 50%, preferably 20% ~ 40%.
The present invention substitutes nitric acid using organic acid or hydracid, and group VIII nitrate, roasting are substituted using there is halogen family salt
Activation process realizes the clean manufacturing of hydrocracking catalyst without NOx emission.
The present invention substitutes nitric acid using hydracid, because hydracid equally has very strong acidity, can prepare high intensity
Hydrocracking catalyst, and price is relatively low, and market obtains easy, will not increase extra preparation cost.
The present invention discharges strong inorganic acid conduct from cleaning for the NOx pollution problems of catalyst preparation process without ammonia nitrogen
Aci-Jel solvent, selection has halogenation group VIII metal salt to substitute nitric acid VIII salt, nitrate anion is eliminated from source dirty
The introducing in dye source, solves the emission problem of difficult pollutant in production.
In the inventive method, by suitable process step, solve and acted on catalyst carrier using metal halide
Power is strong, influences the problem of catalyst performance.
Preparation method of the present invention is simple, it is easy to operate, and the prices of raw materials are cheap, be suitable for various extruded moulding catalyst or
The preparation of carrier, and without particular/special requirement, can just be realized on existing equipment.
Specific embodiment
Below by taking hydrocracking catalyst as an example, a kind of detailed process of catalyst of the present invention is illustrated.
（1）Determine the contents on dry basis of catalyst carrier for hydrgenating material, such as molecular sieve, aluminum hydroxide solid elastomer and amorphous silica-alumina
The contents on dry basis of the materials such as dry glue.A certain amount of said components are weighed in ratio needed for hydrocracking catalyst, is filled in kneading machine
Divide mixing, mixed material is placed in roller, addition concentration is 13.2g acetic acid/100mL and 8.0g β-carboxyethyl acrylic acid
Ester/100mL mixed solutions（4gHCl/100mL can also be used）, rolling to be formed can squeeze paste shape, then extruded moulding, catalysis
Dosage form shape can be column, clover, bunge bedstraw herb and other irregular strips etc., and length controls 3 ~ 8mm.First by wet bar 100 ~ 150
Dried 2 ~ 6 hours under the conditions of DEG C, be then calcined, 400 ~ 600 DEG C of sintering temperature, the time is 2 ~ 10 hours, prepares catalysis
Agent carrier, and determine its water absorption rate.
（2）By taking tungstenic nickel hydrogenation metal catalyst as an example, non-noble is hydrogenated with the preparation of halogen family metal salt solution：Take a certain amount of
Deionized water is warming up to 40 DEG C under stirring, is gradually added into nickel chloride crystal, treats solution clear, adds metatungstic acid
Ammonium crystal, after after all dissolvings, is cooled to normal temperature, filters, and obtains metallic compound dipping solution.With metal oxide in solution
The concentration of meter is generally, WO3Content is 30.0 ~ 55.0gWO3/ 100mL, NiO content are 8.0 ~ 24.0gNiO/100mL.
（3）By step（1）The carrier strip of acquisition, by the solid volume ratio 3 of liquid:It is molten that 1 ratio is added to metallic compound dipping
In liquid, infiltrate 60~240min, dipping rear catalyst is dried 2 ~ 6 hours by filtering under the conditions of 100 ~ 150 DEG C, then with 1~
The ammoniacal liquor of 4mol/L, sal volatile or ammonium bicarbonate solution carry out impregnation process, and solution usage is generally carrier water absorption rate
50%~100%.Then dried 2~48 hours at 50~200 DEG C, be calcined 2~10 hours at 300~600 DEG C.
Modified molecular screen used in carrier of hydrocracking catalyst of the present invention, can with Modified Zeolite Y, beta-molecular sieve,
One or more compound uses of ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieves.The method of modifying of molecular sieve
Can be hydro-thermal process or EDTA, SiCl4、(NH4)2SiF6, the modified method of chemical dealuminization such as phosgene or oxalic acid, and using acid,
Alkali, the hydro-thermal of salt formula complexing agent are combined etc. the molecular sieve of method of modifying treatment with chemical dealuminization.The property of modified molecular screen used
Matter is：Silica is 3 ~ 100, preferably 10 ~ 60, Na with alumina molar ratio2O content≤0.5wt%, meleic acid amount be 0.1 ~
1.2mmol/g, preferably 0.2 ~ 0.6mmol/g.
The general selection of aluminum oxide or amorphous silica-alumina that the present invention is used can select existing goods, and the mL/g of pore volume 0.5 ~
1.8mL/g, specific surface area is 220m2/g~550m2/ g, meleic acid amount is 0.05 ~ 0.70mmol/g.
The following examples are used to illustrate in greater detail the preparation method of carrier of the present invention, but the scope of the present invention is not only limited
In the scope of these embodiments.
The molecular sieve used in embodiment be Modified Zeolite Y 1 be commercially available H types molecular sieve by 500 DEG C of hydro-thermal process 2
Modified Zeolite Y after hour.Modified Zeolite Y 2 is commercially available H types molecular sieve by after 600 DEG C of hydro-thermal process 2 hours,
The Modified Zeolite Y for being processed through EDTA again.
The aluminum hydroxide solid elastomer powder used in embodiment is that Tianjin Tian Jiu companies produce macroporous aluminium oxide（3824 macropores are aoxidized
Aluminium）, 400 DEG C roasting 3 hours after property be pore volume 0.82mL/g, specific surface area 323m2/g。
The contained amorphous silica-alumina dry glue powder used in embodiment is that Tianjin Tian Jiu companies produce amorphous silica-alumina（3903 is amorphous
Sial）, 400 DEG C roasting 3 hours after property be pore volume 0.76mL/g, specific surface area 286m2/ g, meleic acid 0.744mmol/g.
Embodiment 1
Containing Y molecular sieve 15% based on final hydrocracking catalyst weight, containing amorphous silica-alumina 35%, containing nickel oxide 5.0%,
Containing tungsten oxide 22.0%, balance of aluminum oxide selects Above-mentioned catalytic agent preparing raw material：Modified Y molecular sieve 1,3824 aluminium hydroxides are done
Rubber powder and 3903 contained amorphous silica-alumina dry glue powder.
Catalyst preparation process is as follows：By modified Y molecular sieve, aluminum hydroxide solid elastomer powder and contained amorphous silica-alumina dry glue powder, with
And sesbania powder etc. is sufficiently mixed in kneading machine, addition concentration be 13.2g acetic acid/100mL and 8.0g β-propyloic acrylic ester/
100mL mixed acid solutions carry out peptization, are extruded into a diameter of 1.5mm cylindrical types.Then dried 4 hours at 120 DEG C, at 480 DEG C
Lower roasting 3 hours, prepares the catalyst carrier of shaping.
The mixed solution of ammonium metatungstate and nickel chloride is made using distilled water, the catalyst carrier that will be molded is in above-mentioned gold
Dip operation is carried out in category compound mixed solution, then time 120min is dried.Material concentration is after drying
The ammoniacal liquor of 4mol/L carries out impregnation process, and ammonia volume is 90% of material water absorption rate after drying, is then dried again and roasts
Burn, obtain final catalyst.Wherein drying is to be dried 6 hours at 150 DEG C, and roasting is calcined 3 hours at 450 DEG C.Catalyst
Numbering is respectively CAT-1.
Embodiment 2
Organic acid soln is changed to 4gHCl/100mL acid peptizing agents, material concentration is the ammoniacal liquor of 1mol/L after drying
Impregnation process is carried out, ammonia volume is 150% of material water absorption rate after drying, and other processes obtain catalyst volume with embodiment 1
Number be CAT-2.
Embodiment 3
It is remaining containing tungsten oxide 22.0% containing nickel oxide 5.0% containing Y molecular sieve 55% based on final hydrocracking catalyst weight
Measure as aluminum oxide selects Above-mentioned catalytic agent preparing raw material：Modified Y molecular sieve 1,3824 aluminum hydroxide solid elastomer powder.
With embodiment 1, it is CAT-3 to obtain catalyst numbering to preparation method.
Embodiment 4
Containing Modified Zeolite Y 5% based on final hydrocracking catalyst weight, amorphous silica-alumina 38%, containing nickel oxide 5%,
Above-mentioned catalytic agent preparing raw material is selected containing tungsten oxide 22.0%：Modified Y molecular sieve 2,3824 aluminum hydroxide solid elastomer powder and 3903 are without fixed
Shape sial dry glue powder.
Ammoniacal liquor carries out impregnation process and uses concentration instead for the ammonium bicarbonate solution of 4mol/L is processed in preparation method, carbonic acid
Hydrogen ammonia solution consumption be dry after material water absorption rate 50%, the other the same as in Example 1, obtain catalyst numbering be CAT-4.
Comparative example 1
According to the catalyst composition and raw material of embodiment 1, support material is first made catalyst carrier, carrier shaping is used
4.0gHNO3/ 100mL dilute nitric acid solutions load hydrogenation active component, metallic solution as sour peptizing agent using conventional impregnation method
It is the high concentration metal mixed solution that nickel nitrate and ammonium metatungstate are prepared, it is CAT-B1 to obtain catalyst numbering.
Comparative example 2
According to the catalyst composition and raw material of embodiment 3, with reference to comparative example 1, it is CAT-B2 to prepare catalyst numbering.
Comparative example 3
According to the catalyst composition and raw material of embodiment 1, ammoniacal liquor impregnation process is not carried out simply, obtain catalyst for CAT-
B3。
In the present embodiment, each example catalyst carries out instrumental analysis and activity rating to more than.Each example catalyst physico-chemical property
It is shown in Table 1.
The catalyst physico-chemical property of table 1.
| Numbering | CAT-1 | CAT-2 | CAT-3 | CAT-4 | CAT-B1 | CAT-B2 | CAT-B3 |
| Molecular sieve content, % | 15 | 15 | 55 | 5 | 15 | 55 | 15 |
| 22.5 | 21.4 | 23.1 | 24.2 | 23.1 | 20.5 | 21.6 | |
| NiO, wt% | 5.9 | 6.1 | 5.3 | 5.1 | 4.9 | 5.6 | 6.2 |
| 235 | 353 | 375 | 198 | 241 | 364 | 345 | |
| 0.364 | 0.335 | 0.268 | 0.390 | 0.357 | 0.279 | 0.331 | |
| 6.11 | 4.35 | 3.76 | 8.03 | 5.97 | 3.45 | 3.83 | |
| 0.93 | 0.89 | 0.84 | 0.91 | 0.96 | 0.90 | 0.91 | |
| Crushing strength, N/cm | 158 | 199 | 153 | 155 | 229 | 198 | 201 |
Note：RBETFor the average pore diameter that BET method is determined.
Evaluating apparatus carry out conventional presulfurization before activity rating using being carried out on 200mL small hydrogenation devices to catalyst.
Evaluate the raw materials used oil nature of catalyst activity and be shown in Table 2, catalyst reaction performance comparison the results are shown in Table 3.Evaluate CAT-1, CAT-
B1, CAT-B3 have carried out comparative evaluation, and feedstock oil first passes through Hydrobon catalyst bed and then immediately proceeds to be hydrocracked urges
Agent bed, controls the organic nitrogen content in feedstock oil to be less than 10 μ g/g during by Hydrobon catalyst bed.
The raw material oil nature of table 2.
| 0.9114 | |
| Boiling range/DEG C | |
| IBP/10% | 328/376 |
| 30%/50% | 400/430 |
| 70%/90% | 455/499 |
| 95%/FBP | 524/542 |
| Condensation point/DEG C | 33 |
| 1.4768 | |
| Carbon residue, weight % | 0.30 |
| S, weight % | 1.60 |
| N, weight % | 0.1175 |
The catalyst reaction performance comparison evaluation result of table 3.
| Catalyst | CAT-1 | CAT-B1 | CAT-B3 |
| Process conditions | |||
| Reaction pressure, MPa | 15.7 | 15.7 | 15.7 |
| 1.5 | 1.5 | 1.5 | |
| Hydrogen to oil volume ratio | 1500:1 | 1500:1 | 1500:1 |
| Control conversion ratio, wt% | 70 | 70 | 70 |
| <10 | <10 | <10 | |
| Cracking zone reaction temperature/DEG C | 356 | 357 | 355 |
| Product slates and product property | |||
| Light naphthar yield, % | 3.3 | 3.1 | 3.5 |
| Heavy naphtha yield, % | 33.6 | 30.2 | 31.7 |
| Heavy naphtha virtue is latent, % | 56.8 | 58.8 | 58.4 |
| Jet fuel yield, % | 21.5 | 23.7 | 21.2 |
| Jet fuel smoke point/mm | 27 | 27 | 24 |
| Diesel yield, % | 9.8 | 11.3 | 10.3 |
| Diesel fuel cetane index | 74.4 | 72.2 | 70.5 |
| Tail oil yield, % | 30.2 | 30.1 | 30.1 |
| Tail oil BMCI values | 9.2 | 9.5 | 13.2 |
It is seen from the above data that catalyst prepared by the inventive method has good performance, while production
During there is no difficult pollutant emission problem.
Claims (14)
1. a kind of preparation method of hydrogenation catalyst, it is characterised in that including following content：
（1）Prepare catalyst carrier；
（2）Metal compound solution containing hydrogenation active component is prepared, hydrogenation active component metallic compound is by group vib metal compound
One or more compositions of one or more and group VIII metal compound of thing, wherein group vib metallic compound uses ammonium salt
Or acidic oxide, group VIII metal compound uses soluble halide；
（3）Using step（2）Preparing metal compound solution impregnation steps（1）Carrier, the material after dipping is dried,
Then impregnation process is carried out using ammoniacal liquor, sal volatile or ammonium bicarbonate soln, finally dry, roasting obtains catalyst product
Product.
2. method according to claim 1, it is characterised in that：Group vib metallic compound be selected from W and Mo compounds in extremely
Few one kind, group VIII metal compound is selected from least one in Ni and Co compounds.
3. method according to claim 1, it is characterised in that：Step（1）In the preparation process of catalyst carrier, selection is carried
Body material, by mixing, shaping, dries and roasting preparation process, obtains catalyst carrier.
4. the method according to claim 1 or 3, it is characterised in that：Carrier material at least includes a kind of acid cracking material,
Acid cracking material includes molecular sieve or amorphous acidic components.
5. method according to claim 4, it is characterised in that：Based on weight content in final catalyst, acid cracking material
Material content is 1%~60%, and the weight content that hydrogenation active component is counted in the catalyst with oxide is 15%~50%.
6. method according to claim 5, it is characterised in that：Based on weight content in final catalyst, acid cracking material
Material content is 5%~40%, and the weight content that hydrogenation active component is counted in the catalyst with oxide is 20%~40%.
7. method according to claim 1, it is characterised in that：Step（1）Peptization is used in catalyst carrier preparation process
Agent or binding agent, peptizing agent are one kind or mixed acid of formic acid, acetic acid, ethanedioic acid, citric acid and/or phosphoric acid, or use halogen
Race's strong acid, binding agent is by the small porous aluminum oxide of peptization.
8. method according to claim 1, it is characterised in that：Step（2）In metallic compound containing hydrogenation active component
In solution, group vib metallic compound be selected from molybdic acid, para-molybdic acid, molybdate, paramolybdate, wolframic acid, metatungstic acid, ethyl metatungstic acid,
At least one in tungstates and metatungstate；Group VIII metal species is nickel and/or cobalt, using chloride or bromide.
9. method according to claim 1, it is characterised in that：Step（2）In be added as needed on suitable adjuvant component,
Adjuvant component is one or more in P, F, B, Zr, Ti.
10. method according to claim 1, it is characterised in that：Step（3）Ammoniacal liquor, sal volatile or ammonium hydrogen carbonate
During the impregnation process of solution, the concentration of solution is 0.5~6mol/L.
11. methods according to claim 10, it is characterised in that：Step（3）Ammoniacal liquor, sal volatile or ammonium hydrogen carbonate
During the impregnation process of solution, the concentration of solution is 1~4mol/L.
12. method according to claim 1 or 10, it is characterised in that：Step（3）Ammoniacal liquor, sal volatile or carbonic acid
During the impregnation process of hydrogen ammonium salt solution, solution usage is the 30%~200% of carrier water absorption rate.
13. methods according to claim 12, it is characterised in that：Step（3）Ammoniacal liquor, sal volatile or ammonium hydrogen carbonate
During the impregnation process of solution, solution usage is the 50%~100% of carrier water absorption rate.
14. methods according to claim 1, it is characterised in that：Step（3）Middle drying dries 2~48 at 50~200 DEG C
Hour, roasting is calcined 2~10 hours at 300~600 DEG C.
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| CN106807418B (en) * | 2017-03-09 | 2019-07-02 | 武汉凯迪工程技术研究总院有限公司 | Hydrotreating catalyst dipping solution and preparation method thereof |
| CN109569699B (en) * | 2017-09-29 | 2021-11-16 | 中国石油化工股份有限公司 | Vulcanized hydrogenation catalyst, and preparation method and application thereof |
| CN114433193B (en) * | 2020-10-30 | 2023-12-12 | 中国石油化工股份有限公司 | Catalyst carrier, hydrogenation catalyst and method for producing low-freezing diesel oil |
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| CN101015803A (en) * | 2007-02-07 | 2007-08-15 | 江苏工业学院 | Catalyst and preparing method thereof, and use in hydrogenation-dechlorination of carbon tetrachloride |
| CN101239318A (en) * | 2008-03-13 | 2008-08-13 | 南开大学 | Cinnamic aldehyde hydrocatalyst and preparation thereof |
| CN102125864A (en) * | 2010-12-16 | 2011-07-20 | 昆明理工大学 | Supported catalyst for hydrogenation of alpha-pinene and preparation method and uses thereof |
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| US7261805B2 (en) * | 1999-02-24 | 2007-08-28 | Exxonmobil Research And Engineering Company | Process for catalytic dewaxing and catalytic cracking of hydrocarbon streams |
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| CN103100404B (en) * | 2011-11-11 | 2015-01-14 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
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| CN101015803A (en) * | 2007-02-07 | 2007-08-15 | 江苏工业学院 | Catalyst and preparing method thereof, and use in hydrogenation-dechlorination of carbon tetrachloride |
| CN101239318A (en) * | 2008-03-13 | 2008-08-13 | 南开大学 | Cinnamic aldehyde hydrocatalyst and preparation thereof |
| EP2540392A1 (en) * | 2010-02-25 | 2013-01-02 | Petrochina Company Limited | Hydro refining catalyst |
| CN102125864A (en) * | 2010-12-16 | 2011-07-20 | 昆明理工大学 | Supported catalyst for hydrogenation of alpha-pinene and preparation method and uses thereof |
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