CN104646048A - Preparation method of hydrogenation catalyst - Google Patents
Preparation method of hydrogenation catalyst Download PDFInfo
- Publication number
- CN104646048A CN104646048A CN201310584178.0A CN201310584178A CN104646048A CN 104646048 A CN104646048 A CN 104646048A CN 201310584178 A CN201310584178 A CN 201310584178A CN 104646048 A CN104646048 A CN 104646048A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acid
- preparation
- carrier
- roasting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a preparation method of a hydrocracking catalyst. The preparation method includes following steps: (1) preparing a catalyst carrier; (2) preparing a metal compound solution containing a hydrogenation active component, herein the hydrogenation active component is one or more of compounds of metals in the VIB group and the VIII group, wherein the VIB metal compound is an ammonium salt oxide or an acidic oxide and the VIII metal compound is a dissolvable halide; and (3) impregnating the catalyst carrier prepared in the step (1) in the metal compound solution prepared in the step (2), drying an impregnated material, regulating properties of the material, and finally drying and roasting the material to obtain the catalyst. The preparation method can solve a problem of discharge of pollutant being difficult to treat during a production process of the hydrocracking catalyst and additionally can further improve the performances of the catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogenation catalyst, especially in preparation process without the preparation method of the hydrogenation catalyst of NOx emission.
Technical background
Hydrogen addition technology is hydrocracking technology particularly, have that adaptability to raw material is strong, the feature such as production operation and products scheme flexibility is large, good product quality, various heavy inferior charging 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, become one of modern oil refining and petro chemical industry most important heavy oil deep processing technique, obtain increasingly extensive application at home and abroad.The key of hydrocracking technology is hydrocracking catalyst, and the raising of its level depends on the exploitation of high-performance catalyst for hydrocracking.External hydrocracking catalyst exploitation patent business mainly contains CLG company, Uop Inc., Criterion catalyst Co., Haldor Topsoe company, Albemarle company and Axens company etc.China is one of country grasping distillate hydrocracking technology the earliest in the world.Along with the sustainable development of national economy, hydrocracking unit working ability improves constantly, and existing disposal ability is more than 50.0Mt/a.Through the effort that domestic several generations hydrogenation scientific and technical personnel are long-term and unremitting, developed A wide selection of colours and designs, the hydrocracking catalyst of series matching and technology, and be industrially widely applied, meet the needs of China's oil refining and chemical engineering industry development very well.
The geometric shape of catalyst and physical dimension, have impact to fluid resistance, air velocity, the distribution of bed temperature gradient, concentration gradient distribution etc.In order to give full play to its catalysis potentiality, should select optimum profile and size, this just needs to select most suitable forming method.The forming method of hydrocracking catalyst mainly contains touches plate, compressing tablet, spin, oil ammonia column balling-up and extrusion etc., and wherein extruded moulding technology is most widely used.Need to add a certain amount of adhesive or diluted acid peptizing agent in extruded moulding process, cementation is played in effect, ensures that shaping rear catalyst has certain geometry appearance shape and higher withstand voltage, scuff resistance.The preparation of adhesive, mainly by diluted acid and alumina dry glue Homogeneous phase mixing according to a certain percentage, obtains jelly through stirring, ageing.Due to nitric acid have acid strong, easily decompose, price is low, and the advantage such as noresidue in the catalyst after decomposing, be to prepare the sour peptizing agent that hydrocracking catalyst the most often uses.Such as CN00110016.5 and CN00123221.5 describes two kinds of oil refining class loaded catalyst extruded moulding methods respectively and all selects nitric acid as Aci-Jel solvent, and US7,687,676 Ludox or Alumina gel directly using nitric acid acidifying are as the adhesive in shaping of catalyst process.
Hydrocracking catalyst preparation method is varied, wherein most importantly infusion process, coprecipitation method, kneading method and ion-exchange etc., and these preparation methods are in the extensive use of hydrogenation catalyst production field.Wherein infusion process is widely used in the preparation of hydrocracking catalyst.Infusion process prepares hydrocracking catalyst, and preparation process requires that hydrogenation metal salt can make good stability, metal salt solution that concentration is high.Hydrocracking catalyst belongs to fine chemical product, complicated process of preparation, and production process is subject to many factors restriction.The hydrogenation activity of hydrocracking catalyst to derive from the periodic table of elements metal component in VI B race and VIII race, and most widely used is W, Mo, Ni, Co tetra-kinds of elements.Wherein nickel (or cobalt) is the most frequently used metal promoter component of hydrocracking catalyst.In order to ensure materialization and the catalytic performance of hydrocracking catalyst, in its preparation process, require the metallic salt of introducing after Roasting Decomposition except oxygen element, residual without other element.When adopting infusion process and coprecipitation method to prepare hydrocracking catalyst, also need to configure that concentration is high, the metal compound solution of good stability.In the compound of nickel metal (or cobalt), nitrate has the advantages such as solubility is high, stability of solution good, the rear noresidue of decomposition, is widely used in hydrocracking catalyst preparation process.CN96109702.7 provides a kind of co-impregnated solution preparing high-activity hydrocracking catalyst, by ammonium metatungstate, a kind of leaching agent of nickel nitrate, obtain obvious lifting by the carrier prepared catalyst performance of this co-impregnated solution dipping containing Y zeolite, refractory inorganic oxides.
CN97121663.0 gives a kind of beta-zeolite molecular sieve catalyst and preparation method thereof, the adhesive using the aluminum oxide precursor thing (boehmite) of nitric acid and little pore volume to prepare in the preparation process of catalyst carries out extruded moulding, the method of the impregnated with nitrate of group VIII metal element is then adopted, although obtain good effect on catalyst strength and reactivity worth in metal adding procedure.But hydrocracking catalyst patent described above, shaping with in hydrogenation metal adding procedure at hydrocracking catalyst, all need to use nitric acid and nickel nitrate in a large number, these nitrate ions decomposes in roasting process, discharge a large amount of NOx, causing suitable harm, is one of key factor of restriction hydrocracking catalyst production.NOx is a kind of important air environmental pollution thing, is to form one of acid rain, photochemical fog and the primary pollution source causing ozone hole.In addition, the generation of a large amount of NOx also can cause heavy corrosion to production equipment and cause very big infringement to operator ' s health.According to statistics, 1 ton of hydrocracking catalyst is often produced by generation about 45 standard cubic meter NOx.Whole world hydrocracking catalyst annual production nearly ten thousand tons, and the hydrotreatment similar to hydrocracking catalyst and the whole world annual production of hydrofinishing class catalyst surprising especially, the pollution that its production process causes atmospheric environment, is subjected to increasing concern.
Increasingly strict along with environmental law, solves the NO in catalyst preparation process
xpollution problem more and more receives concern.In order to cleaning of catalyst production process, people have selected some clean raw material without ammonia nitrogen discharge in catalyst preparation process.In hydrocracking catalyst preparation process, selection can meet the clean acids of catalyst preparation process and physical and chemical performance requirement as peptizing agent, and the metallic salt to produce without NOx is as the substitute of nitrate, is the key problem in technology cleaned realizing hydrocracking catalyst preparation process.CN00110016.5 and CN00123221.5 describes two kinds of oil refining class loaded catalyst extruded moulding methods respectively.In the selection of Aci-Jel solvent, except nitric acid can be used as Aci-Jel solvent, two schemes all have employed more inorganic and organic acid and selects, as inorganic acid can select the combination of phosphoric acid, hydrochloric acid, sulfuric acid or several acid, organic acid can formic acid, acetic acid, oxalic acid, citric acid etc.But all there is the impurities left problems such as Cl, S, P after these inorganic acid decomposes, be not suitable as the peptizing agent of shaping of catalyst; Organic acid then because its acidity more weak be difficult to meet prepare high mechanical properties requirement catalyst or carrier.CN201010211884.7 then gives the metallic solution adopting the metal mixed solution of water miscible organic acid nickel salt preparation to flood as hydrocracking catalyst, the catalyst towards heavy aromatic hydrocarbons prepared has obvious catalyzed conversion ability, these organic nickel salts can be nickel acetate, nickel formate, citric acid nickel, ethanedioic acid nickel etc., adopt organic nickel salt to substitute nickel nitrate, the clean production of hydrocracking catalyst metal adding procedure can be realized.But, according to the data that " handbook of inorganic chemistry " is inquired about, and simulate the experiment of this patent, the solubility of organic nickel salt is all lower, as 25 DEG C of the four water acetic acid nickel solubility in water is only 16.0g tetra-water acetic acid nickel/100mL(4.9gNiO/100mL), be difficult to the metal salt solution making high-concentration stable, be difficult to meet the requirement that conventional infusion process prepares hydrocracking catalyst.And some other inorganic acid VIII salt, although have higher solubility, as the group VIII metal salt of halogen family, sulfuric acid etc., the active force of group VIII metal halogen family salt and carrier is comparatively strong, and the Hydrogenation of catalyst is affected.
Summary of the invention
For halogen family strong acid group VIII metal salt, there is higher solubility, roasting process is without NOx emission, clean Kaolinite Preparation of Catalyst requirement can be met, but the active force added between active metal component and carrier, reduce Hydrogenation, the present invention solves and solves this problem by post-processing approach, improves the serviceability of catalyst, and realizes the clean preparation of hydrogenation catalyst.
Hydrogenation catalyst preparation method process of the present invention comprises following content:
(1) Kaolinite Preparation of Catalyst carrier;
(2) preparation is containing hydrogenation active component metal compound solution, by one or more of hydrogenation active component group vib and VIII metallic compound, group vib metallic compound is selected from least one in W and Mo compound, and VIII metallic compound is selected from least one in Ni and Co compound; Wherein vib metal compound adopts ammonium salt or acidic oxide, and VIII metallic compound adopts soluble halide;
(3) carrier of step (2) preparing metal compound solution impregnation steps (1) is adopted, drying is carried out to the material after dipping, then adopt ammoniacal liquor, sal volatile or ammonium bicarbonate soln to carry out impregnation process, final drying, roasting obtain catalyst prod.
In the present invention, the preparation of step (1) catalyst carrier can adopt this area conventional method, selects carrier material according to the requirement of catalyst property, through preparation process such as mixing, shaping, dry and roastings, obtains catalyst carrier.For hydrocracking catalyst, carrier material at least comprises a kind of acidic cracking components; Prepare carrier of hydrocracking catalyst, by acid carrier component as modified molecular screen, macroporous aluminium oxide powder and/or contained amorphous silica-alumina dry glue powder, and other extrusion aid, after the mixture such as expanding agent, lubricant is fully dry mixed, add organic acid or halogen family strong acid adhesive carries out shaping, extrusion, banded extruder orifice plate can be cylindrical, clover, bunge bedstraw herb or other is special-shaped, then carries out low temperature drying, high-temperature roasting activates, and prepares the carrier of hydrocracking catalyst of high strength.
Acid cracking material of the present invention comprises molecular sieve or amorphous acidic components, molecular sieve generally comprises one or more in Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve etc., and amorphous acidic components are generally one or more in amorphous aluminum silicide, amorphous silicon magnesium and clay etc.Required molecular sieve can require according to serviceability the modification carrying out being suitable for.In hydrocracking catalyst, carrier material can also comprise acid more weak inorganic refractory oxide, is generally aluminium oxide or containing auxiliary agent aluminium oxide, during use generally with aluminum hydroxide solid elastomer powder for raw material.The raw material with large pore volume, bigger serface in the preferred this area such as amorphous acidic components and aluminium oxide.By weight content in final catalyst, the general content of acid cracking material is 1% ~ 60%, and be preferably 5% ~ 40%, hydrogenation active component is generally 15% ~ 50% with oxide basis weight content in the catalyst, be preferably 20% ~ 40%, simultaneously can also salic less than 50%.
Peptizing agent is generally acid solution in step (1), and as one or the mixed acid of the organic acids such as formic acid, acetic acid, ethanedioic acid, citric acid and/or phosphoric acid, also can adopt inorganic halogen family strong acid, binding agent is generally the little porous aluminum oxide through peptization.Shapingly can to determine according to the shape of final catalyst, as cylinder, clover, bunge bedstraw herb, irregular strip etc.The sintering temperature of catalyst carrier is generally 300 ~ 600 DEG C, and roasting time is generally 2 ~ 10 hours.
In step (2) containing hydrogenation active component metal compound solution in, group vib metallic compound can be selected from least one in molybdic acid, para-molybdic acid, molybdate, paramolybdate, wolframic acid, metatungstic acid, ethyl metatungstic acid, tungstates and metatungstate, wherein preferred ammonium paramolybdate and/or metatungstic acid ammonium salt.Group VIII metal kind is nickel and/or cobalt mainly, and it has inorganic strong acid salt class can be chloride or bromide etc., preferred chloride.
Suitable adjuvant component can be added as required, as contained the compound of one or more in P, F, B, Zr, Ti etc. in dipping solution in step (2).
Step (3) ammoniacal liquor, sal volatile or ammonium bicarbonate soln spray in processing procedure, the concentration of solution is generally 0.5 ~ 6mol/L, be preferably 1 ~ 4mol/L.Solution usage is generally 30% ~ 200% of material water absorption rate, is preferably 50% ~ 100%.Drying in step (3) and roasting can adopt normal condition, dry general at 50 ~ 200 DEG C dry 2 ~ 48 hours, roasting generally roasting 2 ~ 10 hours at 300 ~ 600 DEG C.
Hydrogenation catalyst prepared by the inventive method has following character, and specific area is 120m
2/ g ~ 450m
2/ g, is preferably 160m
2/ g ~ 400m
2/ g; Pore volume is 0.20cm
3/ g ~ 0.50cm
3/ g, is preferably 0.30cm
3/ g ~ 0.45cm
3/ g, hydrogenation metal total content is 15% ~ 50%, is preferably 20% ~ 40%.
The present invention adopts organic acid or hydracid to substitute nitric acid, and use and have halogen family salt to substitute group VIII nitrate, calcination activation process, without NOx emission, achieves the cleaner production of hydrocracking catalyst.
The present invention adopts hydracid to substitute nitric acid, because hydracid has very strong acidity equally, can prepare the hydrocracking catalyst of high strength, and price is relatively low, and market obtains easily, can not increase extra preparation cost.
The present invention is directed to the NOx pollution problem of catalyst preparation process, select and clean without ammonia nitrogen discharge strong inorganic acid as Aci-Jel solvent, selection has halogenation group VIII metal salt to substitute nitric acid VIII salt, eliminate the introducing of nitrate anion pollution sources from source, solve the emission problem of difficult pollutant in production.
In the inventive method, by suitable treatment step, solve and use metal halide and catalyst carrier active force by force, affect the problem of catalyst serviceability.
Preparation method of the present invention is simple, and be easy to operation, the prices of raw and semifnished materials are cheap, are suitable for the preparation of various extruded moulding catalyst or carrier, and without particular/special requirement, existing equipment just can realize.
Detailed description of the invention
Below for hydrocracking catalyst, illustrate a kind of detailed process of catalyst of the present invention.
(1) contents on dry basis of catalyst carrier for hydrgenating material is measured, as the contents on dry basis of the materials such as molecular sieve, aluminum hydroxide solid elastomer and contained amorphous silica-alumina dry glue.A certain amount of said components is taken in ratio needed for hydrocracking catalyst, fully mix in kneading machine, mixed material is placed in roller, adding concentration is 13.2g acetic acid/100mL and 8.0g β-propyloic acrylic ester/100mL mixed solution (also can adopt 4gHCl/100mL), roll formation and can squeeze paste shape, then extruded moulding, catalyst shape can be column, clover, bunge bedstraw herb and other irregular strip etc., cut to lengthen 3 ~ 8mm.First will wet bar under 100 ~ 150 DEG C of conditions dry 2 ~ 6 hours, and then carry out roasting, sintering temperature 400 ~ 600 DEG C, the time is 2 ~ 10 hours, prepares catalyst carrier, and measures its water absorption rate.
(2) for tungstenic nickel hydrogenation metal catalyst, the preparation of non-noble hydrogenation halogen family metal salt solution: get a certain amount of deionized water under stirring, be warming up to 40 DEG C, add nickel chloride crystal gradually, treat solution clear, add ammonium metatungstate crystal, after all dissolving, be cooled to normal temperature, filter, obtain metallic compound dipping solution.Concentration with metal oxide in solution is generally, WO
3content is 30.0 ~ 55.0gWO
3/ 100mL, NiO content is 8.0 ~ 24.0gNiO/100mL.
(3) by carrier strip that step (1) obtains, join in metallic compound dipping solution in the ratio of liquid-solid volume ratio 3:1, infiltrate 60 ~ 240min, filter, rear catalyst will be flooded under 100 ~ 150 DEG C of conditions dry 2 ~ 6 hours, then carry out impregnation process with the ammoniacal liquor of 1 ~ 4mol/L, sal volatile or ammonium bicarbonate solution, solution usage is generally 50% ~ 100% of carrier water absorption rate.Then at 50 ~ 200 DEG C dry 2 ~ 48 hours, roasting 2 ~ 10 hours at 300 ~ 600 DEG C.
Modified molecular screen used in carrier of hydrocracking catalyst of the present invention, can one or more compound uses of Modified Zeolite Y, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve.The method of modifying of molecular sieve can be hydrothermal treatment consists or EDTA, SiCl
4, (NH
4)
2siF
6, the chemical dealuminization modification method such as phosgene or oxalic acid, and use acid, alkali, the hydro-thermal of salt formula complexing agent and the molecular sieve of the method for modifying process such as chemical dealuminization combines.The character of modified molecular screen used is: silica and alumina molar ratio are 3 ~ 100, is preferably 10 ~ 60, Na
2o content≤0.5wt%, meleic acid amount is 0.1 ~ 1.2mmol/g, preferably 0.2 ~ 0.6mmol/g.
The aluminium oxide that the present invention uses or amorphous aluminum silicide are generally selected and can be selected existing goods, pore volume 0.5 mL/g ~ 1.8mL/g, and specific area is 220m
2/ g ~ 550m
2/ g, meleic acid amount is 0.05 ~ 0.70mmol/g.
The following examples are for illustrating in greater detail the preparation method of carrier of the present invention, but scope of the present invention is not only limited to the scope of these embodiments.
The molecular sieve used in embodiment for Modified Zeolite Y 1 be that commercially available H type molecular sieve is through the Modified Zeolite Y of 500 DEG C of hydrothermal treatment consists after 2 hours.Modified Zeolite Y 2 be commercially available H type molecular sieve through 600 DEG C of hydrothermal treatment consists after 2 hours, then through the Modified Zeolite Y of EDTA process.
The aluminum hydroxide solid elastomer powder used in embodiment is that Tianjin Tian Jiu company produces macroporous aluminium oxide (3824 macroporous aluminium oxide), 400 DEG C of roastings after 3 hours character be pore volume 0.82mL/g, specific area 323m
2/ g.
The contained amorphous silica-alumina dry glue powder used in embodiment is that Tianjin Tian Jiu company produces amorphous aluminum silicide (3903 amorphous aluminum silicide), 400 DEG C of roastings after 3 hours character be pore volume 0.76mL/g, specific area 286m
2/ g, meleic acid 0.744mmol/g.
Embodiment 1
By final hydrocracking catalyst weighing scale containing Y molecular sieve 15%, containing amorphous aluminum silicide 35%, containing nickel oxide 5.0%, containing tungsten oxide 22.0%, surplus is that Above-mentioned catalytic agent raw materials selected by aluminium oxide: modified Y molecular sieve 1,3824 aluminum hydroxide solid elastomer 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, and sesbania powder etc. fully mixes in kneading machine, adding concentration is that 13.2g acetic acid/100mL and 8.0g β-propyloic acrylic ester/100mL mixed acid solution carries out peptization, and being extruded into diameter is 1.5mm column type.Then at 120 DEG C dry 4 hours, at 480 DEG C, roasting 3 hours, prepared shaping catalyst carrier.
Adopt distilled water to make the mixed solution of ammonium metatungstate and nickel chloride, shaping catalyst carrier is carried out dip operation in above-mentioned metallic compound mixed solution, time 120min, then carry out drying.Dry rear material working concentration is that the ammoniacal liquor of 4mol/L carries out impregnation process, and ammonia volume is 90% of dry rear material water absorption rate, and then carries out drying and roasting, obtains final catalyst.Wherein drying is at 150 DEG C dry 6 hours, roasting roasting 3 hours at 450 DEG C.Catalyst numbering is respectively CAT-1.
Embodiment 2
Organic acid soln is changed into 4gHCl/100mL acid peptizing agent, dry rear material working concentration is that the ammoniacal liquor of 1mol/L carries out impregnation process, and ammonia volume is 150% of dry rear material water absorption rate, and other process, with embodiment 1, obtains catalyst and is numbered CAT-2.
Embodiment 3
By final hydrocracking catalyst weighing scale containing Y molecular sieve 55%, containing nickel oxide 5.0%, containing tungsten oxide 22.0%, surplus is that Above-mentioned catalytic agent raw materials selected by aluminium oxide: modified Y molecular sieve 1,3824 aluminum hydroxide solid elastomer powder.
Preparation method, with embodiment 1, obtains catalyst and is numbered CAT-3.
Embodiment 4
By final hydrocracking catalyst weighing scale containing Modified Zeolite Y 5%, amorphous aluminum silicide 38%, containing nickel oxide 5%, select Above-mentioned catalytic agent raw materials containing tungsten oxide 22.0%: modified Y molecular sieve 2,3824 aluminum hydroxide solid elastomer powder and 3903 contained amorphous silica-alumina dry glue powder.
In preparation method, ammoniacal liquor carries out impregnation process to use concentration instead is that the ammonium bicarbonate solution of 4mol/L processes, ammonium bicarbonate solution consumption be dry after material water absorption rate 50%, the other the same as in Example 1, obtains catalyst and is numbered CAT-4.
Comparative example 1
According to catalyst composition and the raw material of embodiment 1, first support material is made catalyst carrier, carrier shaping use 4.0gHNO
3/ 100mL dilute nitric acid solution, as sour peptizing agent, adopts conventional infusion process load hydrogenation active component, and metallic solution is the high concentration metal mixed solution that nickel nitrate and ammonium metatungstate are prepared, and obtains catalyst and is numbered CAT-B1.
Comparative example 2
According to catalyst composition and the raw material of embodiment 3, with reference to comparative example 1, Kaolinite Preparation of Catalyst is numbered CAT-B2.
Comparative example 3
According to catalyst composition and the raw material of embodiment 1, just do not carry out ammoniacal liquor impregnation process, obtaining catalyst is CAT-B3.
In the present embodiment, instrumental analysis and activity rating are carried out to above each routine catalyst.Each routine catalyst physico-chemical property is shown in Table 1.
Table 1. catalyst physico-chemical property
| 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 |
| WO 3，wt% | 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 |
| S BET，m 2/g | 235 | 353 | 375 | 198 | 241 | 364 | 345 |
| V SIN，ml/g | 0.364 | 0.335 | 0.268 | 0.390 | 0.357 | 0.279 | 0.331 |
| R BET，nm | 6.11 | 4.35 | 3.76 | 8.03 | 5.97 | 3.45 | 3.83 |
| Bulk density, g/cm 3 | 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: R
bETfor the average pore diameter that BET method measures.
Evaluating apparatus adopts on 200mL small hydrogenation device and carries out, and carries out conventional presulfurization before activity rating to catalyst.The raw materials used oil nature of evaluation of catalyst activity is in table 2, and catalyst reaction performance comparison the results are shown in Table 3.Evaluation CAT-1, CAT-B1,
cAT-B3carried out comparative evaluation, then feedstock oil first directly enter hydrocracking catalyst bed through Hydrobon catalyst bed, and the organic nitrogen content in Hydrobon catalyst bed control feedstock oil is lower than 10 μ g/g.
Table 2. feedstock oil character
| Density (20 DEG C)/gcm -3 | 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 |
| Refractive power/n D 70 | 1.4768 |
| Carbon residue, % by weight | 0.30 |
| S, % by weight | 1.60 |
| N, % by weight | 0.1175 |
Table 3. catalyst reaction performance comparison evaluation result
| Catalyst | CAT-1 | CAT-B1 | CAT-B3 |
| Process conditions | |||
| Reaction pressure, MPa | 15.7 | 15.7 | 15.7 |
| Volume space velocity during liquid, h -1 | 1.5 | 1.5 | 1.5 |
| Hydrogen to oil volume ratio | 1500:1 | 1500:1 | 1500:1 |
| Control conversion ratio, wt% | 70 | 70 | 70 |
| Refined oil nitrogen content, μ g/g | <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 dived, % | 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 value | 9.2 | 9.5 | 13.2 |
As can be seen from above-mentioned data, catalyst prepared by the inventive method has good serviceability, does not have difficult pollutant emission problem in production process simultaneously.
Claims (11)
1. a preparation method for hydrogenation catalyst, is characterized in that comprising following content:
(1) Kaolinite Preparation of Catalyst carrier;
(2) preparation is containing hydrogenation active component metal compound solution, and by one or more of hydrogenation active component group vib and VIII metallic compound, wherein vib metal compound adopts ammonium salt or acidic oxide, and VIII metallic compound adopts soluble halide;
(3) carrier of step (2) preparing metal compound solution impregnation steps (1) is adopted, drying is carried out to the material after dipping, then adopt ammoniacal liquor, sal volatile or ammonium bicarbonate soln to carry out impregnation process, final drying, roasting obtain catalyst prod.
2. method according to claim 1, is characterized in that: group vib metallic compound is selected from least one in W and Mo compound, and VIII metallic compound is selected from least one in Ni and Co compound.
3. method according to claim 1, is characterized in that: in the preparation process of step (1) catalyst carrier, selects carrier material, through mixing, shaping, dry and roasting preparation process, obtains catalyst carrier.
4. the method according to claim 1 or 3, is characterized in that: carrier material at least comprises a kind of acidic cracking components, and acid cracking material comprises molecular sieve or amorphous acidic components.
5. method according to claim 4, it is characterized in that: by weight content in final catalyst, acid cracking material content is 1% ~ 60%, is preferably 5% ~ 40%, hydrogenation active component for 15% ~ 50%, is preferably 20% ~ 40% with oxide basis weight content in the catalyst.
6. method according to claim 1, it is characterized in that: in step (1) catalyst support preparation process, use peptizing agent or binding agent, peptizing agent is one or the mixed acid of formic acid, acetic acid, ethanedioic acid, citric acid and/or phosphoric acid, or adopt halogen family strong acid, binding agent is the little porous aluminum oxide through peptization.
7. method according to claim 1, it is characterized in that: containing in the metal compound solution of hydrogenation active component in step (2), group vib metallic compound is selected from least one in molybdic acid, para-molybdic acid, molybdate, paramolybdate, wolframic acid, metatungstic acid, ethyl metatungstic acid, tungstates and metatungstate; Group VIII metal kind is nickel and/or cobalt, adopts chloride or bromide.
8. method according to claim 1, is characterized in that: step adds suitable adjuvant component in (2) as required, and adjuvant component is one or more in P, F, B, Zr, Ti.
9. method according to claim 1, is characterized in that: in the impregnation process process of the ammoniacal liquor of step (3), sal volatile or ammonium bicarbonate soln, the concentration of solution is 0.5 ~ 6mol/L, is preferably 1 ~ 4mol/L.
10. the method according to claim 1 or 9, is characterized in that: in the impregnation process process of the ammoniacal liquor of step (3), sal volatile or ammonium bicarbonate soln, solution usage is 30% ~ 200% of carrier water absorption rate, is preferably 50% ~ 100%.
11. methods according to claim 1, is characterized in that: in step (3) dry at 50 ~ 200 DEG C dry 2 ~ 48 hours, roasting roasting 2 ~ 10 hours at 300 ~ 600 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310584178.0A CN104646048B (en) | 2013-11-20 | 2013-11-20 | A kind of preparation method of hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310584178.0A CN104646048B (en) | 2013-11-20 | 2013-11-20 | A kind of preparation method of hydrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104646048A true CN104646048A (en) | 2015-05-27 |
| CN104646048B CN104646048B (en) | 2017-06-20 |
Family
ID=53237980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310584178.0A Active CN104646048B (en) | 2013-11-20 | 2013-11-20 | A kind of preparation method of hydrogenation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104646048B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106807418A (en) * | 2017-03-09 | 2017-06-09 | 武汉凯迪工程技术研究总院有限公司 | Hydrotreating catalyst dipping solution and preparation method thereof |
| CN106807419A (en) * | 2017-03-09 | 2017-06-09 | 武汉凯迪工程技术研究总院有限公司 | The method that infusion process prepares hydrotreating catalyst |
| CN109569699A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Sulfurized hydrogenation catalyst and its preparation method and application |
| CN114433193A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst carrier, hydrogenation catalyst and method for producing low freezing point diesel oil |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154668A (en) * | 1994-07-29 | 1997-07-16 | 切夫里昂美国公司 | Low macropore resid conversion catalyst |
| US20040004020A1 (en) * | 1999-02-24 | 2004-01-08 | Grove Michael T. | Process for catalytic dewaxing and catalytic cracking of hydrocarbon streams |
| 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 |
| US20090198076A1 (en) * | 2006-09-29 | 2009-08-06 | Scientific Design Company, Inc. | Catalyst with bimodal pore size distribution and the use 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 |
| EP2540392A1 (en) * | 2010-02-25 | 2013-01-02 | Petrochina Company Limited | Hydro refining catalyst |
| CN103100404A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
-
2013
- 2013-11-20 CN CN201310584178.0A patent/CN104646048B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154668A (en) * | 1994-07-29 | 1997-07-16 | 切夫里昂美国公司 | Low macropore resid conversion catalyst |
| US20040004020A1 (en) * | 1999-02-24 | 2004-01-08 | Grove Michael T. | Process for catalytic dewaxing and catalytic cracking of hydrocarbon streams |
| US20090198076A1 (en) * | 2006-09-29 | 2009-08-06 | Scientific Design Company, Inc. | Catalyst with bimodal pore size distribution and the use thereof |
| 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 |
| CN103100404A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106807418A (en) * | 2017-03-09 | 2017-06-09 | 武汉凯迪工程技术研究总院有限公司 | Hydrotreating catalyst dipping solution and preparation method thereof |
| CN106807419A (en) * | 2017-03-09 | 2017-06-09 | 武汉凯迪工程技术研究总院有限公司 | The method that infusion process prepares hydrotreating catalyst |
| CN106807419B (en) * | 2017-03-09 | 2019-07-02 | 武汉凯迪工程技术研究总院有限公司 | The method that infusion process prepares hydrotreating catalyst |
| 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 |
| CN109569699A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Sulfurized hydrogenation catalyst and its preparation method and application |
| 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 |
| CN114433193A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst carrier, hydrogenation catalyst and method for producing low freezing point diesel oil |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104646048B (en) | 2017-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2404667B1 (en) | A hydrocracking catalyst, process for preparing the same and use thereof | |
| CN100496719C (en) | Heavy fractional oil hydrogenation catalyst and production thereof | |
| CN102463131B (en) | Hydrocracking catalyst and preparation method thereof | |
| CN103100400B (en) | Preparation method of hydrocracking catalyst | |
| CN103191773B (en) | Method for preparing hydrocracking catalyst | |
| CN103769179B (en) | A kind of preparation method of catalyst for hydrotreatment of residual oil | |
| CN104646048B (en) | A kind of preparation method of hydrogenation catalyst | |
| CN103191774B (en) | Method for preparing hydrocracking catalyst | |
| CN103785447B (en) | The clean method for preparing of hydrocracking catalyst | |
| CN103785441A (en) | Hydrocracking catalyst, and preparation method and application thereof | |
| CN105709802B (en) | A kind of high metal dispersion degree hydrocracking catalyst and preparation method thereof | |
| CN103785448B (en) | A kind of clean method for preparing of hydrogenation catalyst | |
| CN103785440A (en) | Preparation method for middle distillate type hydrocracking catalyst containing metal nitride | |
| CN104549426B (en) | A kind of method that hydrocracking catalyst is prepared without NOx emission cleaning | |
| CN105709800B (en) | A kind of low NOxThe hydrocracking catalyst preparation method of discharge | |
| CN106179382B (en) | A kind of preparation method of body phase hydrotreating catalyst | |
| CN106179388B (en) | A kind of preparation method of hydrotreating catalyst | |
| CN104549429B (en) | Clean preparation method of hydrocracking catalyst without NOx discharging | |
| CN105713657A (en) | Hydrocracking method | |
| CN104549458B (en) | A kind of maximum produces ethylene raw hydrocracking catalyst and preparation method thereof | |
| CN104646072B (en) | A kind of preparation method of carrier of hydrogenating catalyst | |
| CN105709805A (en) | Chemical hydrocracking catalyst and preparation method thereof | |
| CN103785442B (en) | A kind of metal nitride type hydrocracking catalyst and its preparation method and application | |
| CN1211464C (en) | Heavy raw oil hydrogenating treatment catalyst and its preparing method | |
| CN104646074A (en) | Clean preparation method of hydrogenation catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |