CN104646074A - Clean preparation method of hydrogenation catalyst - Google Patents
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Abstract
The invention relates to a clean preparation method of a hydrocracking catalyst. The clean preparation method includes following steps: (1) selecting a hydrocracking catalyst carrier material powder, wherein a carrier material at least comprising an acidic cracking material; (2) preparing a metal compound solution containing a hydrogenation active component, wherein the hydrogenation active component is one or more of metals in the VIB group and the VIII group; (3) impregnating the catalyst carrier material powder in the metal compound solution, performing filtration, and then performing a drying process and a crushing process to enable the hydrogenation active component to be dispersed in the catalyst carrier material powder; and (4) adding a peptizing agent or a binding agent to the catalyst carrier material powder with the hydrogenation active component dispersed therein, fully roll-grinding the material and moulding the material, and drying and roasting the moulded material to obtain the hydrocracking catalyst. Compared with a preparation method in the prior art, the clean preparation method is reduced in pollutant discharge and can improve performances of the hydrocracking 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 current throughput 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 the catalysis potentiality of catalyst, 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 patent 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 compounds can make good stability, metal compound 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 metals.Wherein metallic nickel (or metallic 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 compound class 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 salt 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 main atmospheric pollutant, 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 compound class 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 compound solution making high-concentration stable, be difficult to meet the requirement that conventional infusion process prepares hydrocracking catalyst.
Summary of the invention
Low for organic acid nickel salt solubility, be difficult to make high-concentration stable metal compound solution, be difficult to meet the deficiency that infusion process prepares hydrocracking catalyst requirement, The present invention gives a kind of by changing hydrogenation catalyst preparation were established, adopt the method for carrier component powder dipping low-concentration organic acid metal compound solution, improve the water absorption rate of carrier, realize the pickup of hydrogenation metal, thus hydrogenation catalyst can be prepared cleanly.
Hydrogenation catalyst preparation process of the present invention comprises following content:
(1) selective hydrogenation catalyst carrier material powder;
(2) preparation is containing the metal compound solution of hydrogenation active component, hydrogenation active component is generally one or more of group vib and VIII metal, with metal compound solution impregnated support material powder, then filters, further drying, pulverizing, hydrogenation active component is dispersed in carrier material powder;
(3) what step (2) obtained has disperseed the carrier material powder of hydrogenation active component to add peptizing agent or binding agent, fully rolls aftershaping, and then dry, roasting obtains catalyst prod.
Preferably, in the inventive method, in order to reduce the active force between carrier and active metal, the material after filtering in step (2) carries out ammonia scrubbing, then carries out drying, pulverization process.
In step of the present invention (1), catalyst carrier for hydrgenating specifically can be determined according to catalyst ground demand.For hydrocracking catalyst, carrier material at least comprises a kind of acid cracking material acid cracking material of the present invention and comprises molecular sieve and/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 acidic support material is 1% ~ 60%, and be preferably 10% ~ 50%, 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%.
In step (2) containing in the metal compound solution of hydrogenation active component, concrete as W, Mo, Ni and Co, wherein VIB is ammonium salt or acidic oxide, and wherein VIII metal adopts it to have water-soluble machine acid salts.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 its organic acid salt can be formates, acetate, oxalate, citrate and tartrate etc., preferred acetate.Above-mentioned metal compound solution is mixed with mixed solution.In above-mentioned metal compound solution, with the group vib metal component content of oxide basis for 5.0 ~ 30.0g/100mL, group VIII metal constituent content 1.0 ~ 5.0gNiO/100mL.
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).
Peptizing agent is generally acid solution in step (3), 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, 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 is generally 300 ~ 600 DEG C, and roasting time is generally 2 ~ 10 hours.
Described ammonia scrubbing can adopt pH value be 8 ~ 14 ammoniacal liquor wash.During washing, ammonia volume is 1 ~ 3 times that waits to wash volume of material.Washing times is 1 ~ 2 time.Wash temperature is 0 ~ 80 DEG C, is preferably 20 ~ 40 DEG C.Wash time is 5 ~ 90 minutes, is preferably 10 ~ 40 minutes.
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%.
Hydrocracking catalyst prepared by the inventive method is for heavy distillate hydrocracking reaction, and optimum produces high-quality heavy naphtha, high-quality jet fuel and high-quality hydrogenation tail oil.Reaction mass carry out hydrocracking last as need the nitrogen content of the organonitrogen compound in raw material to be removed to lower than 50 μ g/g, preferably lower than 20 μ g/g, most preferably lower than 10 μ g/g.The operating condition of hydrocracking reaction is generally hydrogen dividing potential drop 3 ~ 20MPa, and reaction temperature is 320 ~ 420 DEG C, and during liquid, volume space velocity is 0.5 ~ 3h
-1, hydrogen to oil volume ratio is 500:1 ~ 3000:1.Actual conditions can adjust according to this area Conventional wisdom according to feedstock property and distribution of reaction products and quality requirement.
The present invention adopts organic acid to substitute inorganic acid, uses organo-metallic compound class to substitute nitric acid nickel salt, and calcination activation process is without NOx emission, and after decomposing, free from admixture remains, and achieves the cleaner production of hydrocracking catalyst.
The inventive method adopts the method for carrier of hydrocracking catalyst material powder dipping hydrogenation active component, compared with the shaping rear carrier impregnation of routine, carrier material powder dipping can absorb more maceration extract, and pick up improves several times than shaping rear carrier pick up.Therefore, maceration extract does not need higher metal concentration, just can prepare the final catalyst prod that active metallic content is higher, and being applicable to very much cannot the dipping of active metallic compound class of compounding high concentration metallic solution.Due to the dipping solution of higher concentration, solution preparation is simple, stable in properties, is applicable to commercial scale and uses.Rarer metallic compound maceration extract can reduce the viscosity of solution, reduces solution surface tension, can weaken the impact of capillary drag phenomena in dipping process like this.Not only can ensure that in catalyst, metal component has higher content, the decentralization of metal at carrier surface can also be improved further.Flood with dusty material before carrier is shaping, the active force between active metal component and carrier component is easily caused to strengthen, Hydrogenation is reduced, in the inventive method, after impregnated activated component, by ammonia scrubbing, have adjusted active metal component and the active force between carrier component and Cracking Component after roasting, efficiently solve above-mentioned deficiency, improve the serviceability of catalyst further.
The present invention is directed to the NOx pollution problem of catalyst preparation process, select clean nitrogenfree oxide discharges, free from admixture is residual organic acid as Aci-Jel solvent, organic acid metal compounds is selected to substitute Nitrates, the introducing of nitrate anion pollution sources is eliminated from source, prepare organic acid adhesive, the preparation process of hydrogenation class catalyst and catalyst carrier can be widely used in.
The present invention, due to the organic acid that adds and organic compound, decomposes volatilization after baking, can play certain reaming effect, can also improve specific area, thus have active influence to the activation plays of catalyst.
In the preparation process of hydrocracking catalyst of the present invention, maceration extract can recycle.Preparation method 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
A kind of detailed process of hydrocracking catalyst of the present invention is as follows:
(1) for tungstenic nickel hydrogenation metal catalyst, the preparation of non-noble hydrogenation organo-metallic solutions: get appropriate deionized water under stirring, be warming up to 60 DEG C, add nickel acetate crystal gradually, treat solution clear, add ammonium metatungstate crystal, after all dissolving, cooling, static, filter, obtain metal impregnation solution, wherein with WO
3the concentration of meter controls to be 5.0 ~ 30.0gWO
3/ 100mL, controls as 1.0 ~ 5.0gNiO/100mL in the concentration of NiO.
(2) contents on dry basis of carrier of hydrocracking catalyst 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.Take said components in ratio needed for hydrocracking catalyst, be placed in and stir metal impregnation solution, solid-to-liquid ratio is 1:5 ~ 1:20(volume ratio), beating time is 10 ~ 120min.Mixed serum carries out suction filtration, and filter cake weight butt controls 10% ~ 35%, and drying 2 ~ 10 hours under 90 ~ 150 DEG C of conditions, the powder butt (weight) containing hydrogenation metal component is 40% ~ 80%, then pulverizes, granularity control 100 ~ 200 order.Preferably carry out ammonia scrubbing step after filtration with before drying.In the application, after butt refers to 500 DEG C of roastings, surplus materials accounts for the percentage of gross weight before roasting.
(3) powder of dispersion hydrogenation metal component step (2) obtained rolls, adding concentration after 20 ~ 60min is 13.2g acetic acid/100mL and 8.0g β-propyloic acrylic ester/100mL mixed solution, continue to roll formation and can squeeze paste shape, then extruded moulding, catalyst shape can be column, clover, bunge bedstraw herb and other different in nature bar etc., cut to lengthen 3 ~ 8mm.
(4) by the carrier strip that step (3) obtains, first under 100 ~ 150 DEG C of conditions dry 2 ~ 6 hours, then carry out roasting, sintering temperature 400 ~ 600 DEG C, the time was 2 ~ 10 hours, prepares finished catalyst.
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, the hydrothermal dealumination of alkali or 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 present invention selects metallic compound class solution, is generally group vib and group VIII metal compounds, and as one or more of the saline solution of the metals such as W, Mo, Ni, Co, VIII metallic compound is water-soluble organic acid salt.1.0 ~ 20g/100mL is preferably with the concentration of metal oxide in solution.
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 macroporous aluminium oxide (3824) that the aluminum hydroxide solid elastomer powder used in embodiment is produced for Tianjin Tian Jiu company, 400 DEG C of roastings after 3 hours character be pore volume 0.82mL/g, specific area 323m
2/ g.
The amorphous aluminum silicide (3903) that the contained amorphous silica-alumina dry glue powder used in embodiment is produced for Tianjin Tian Jiu company, 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, aluminum hydroxide solid elastomer powder and contained amorphous silica-alumina dry glue powder.
Catalyst preparation process is as follows: Y molecular sieve, aluminum hydroxide solid elastomer powder and contained amorphous silica-alumina dry glue powder are fully mixed, the metallic compound mixed solution prepared with nickel acetate and ammonium metatungstate is pulled an oar and is flooded, dip time 120min, suction filtration, drying 4 hours at 120 DEG C, then pulverize, to sieve to obtain powder with 180 orders.
Mixed with appropriate extrusion aid sesbania powder by powder, 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, roasting 3 hours at 480 DEG C, catalyst numbering was respectively HC-1.
Embodiment 2
By final hydrocracking catalyst weighing scale containing Y molecular sieve 40%, containing amorphous aluminum silicide 15%, 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.
Preparation method, with embodiment 1, obtains catalyst and is numbered HC-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 HC-3.
Embodiment 4
By final hydrocracking catalyst weighing scale containing Modified Zeolite Y 5%, amorphous aluminum silicide 38%, containing nickel oxide 5.0%, 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.
Preparation method, with embodiment 1, obtains catalyst and is numbered HC-4.
Embodiment 5
According to catalyst composition and the raw material of embodiment 1, in preparation method, metal compound solution mix with carrier material pull an oar, flood, after suction filtration, employing pH value be 10 ammoniacal liquor wash, during washing, ammonia volume is 2 times that treat washing volume of material.Washing times is 1 time.Wash temperature is 30 DEG C.Wash time is 15 minutes.Then carry out drying, other step and condition, with embodiment 1, obtain catalyst and are numbered HC-5.
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 HC-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 HC-B2.
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
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.Evaluate HC-1, HC-5 and HC-B1 and carried 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
Table 3. catalyst reaction performance comparison evaluation result
As can be seen from response data, catalyst prepared by the inventive method has better Hydrogenation, is embodied in heavy naphtha yield higher, and jet fuel smoke point is higher, and diesel fuel cetane index is higher, and tail oil BMCI value is lower.
Claims (12)
1. a clean method for preparing for hydrogenation catalyst, is characterized in that comprising following content:
(1) selective hydrogenation catalyst carrier material powder;
(2) preparation is containing the metal compound solution of hydrogenation active component, hydrogenation active component is one or more of group vib and VIII metal, with metal compound solution impregnated support material powder, then filters, carry out drying, pulverizing further, hydrogenation active component is dispersed in carrier material powder;
(3) what step (2) obtained has disperseed the carrier material powder of hydrogenation active component to add peptizing agent or binding agent, fully rolls aftershaping, and then dry, roasting obtains catalyst prod.
2. method according to claim 1, is characterized in that: the material after filtering in step (2) carries out ammonia scrubbing, then carries out drying, pulverization process.
3. method according to claim 1, it is characterized in that: acid cracking material comprises molecular sieve and/or amorphous acidic components, molecular sieve comprises one or more in Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve, and amorphous acidic components are one or more in amorphous aluminum silicide, amorphous silicon magnesium and clay.
4. the method according to claim 1 or 3, it is characterized in that: by weight content in final catalyst, acidic support material content is 1% ~ 60%, is preferably 10% ~ 50%, hydrogenation active component for 15% ~ 50%, is preferably 20% ~ 40% with oxide basis weight content in the catalyst.
5. 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, and its organic acid salt is formates, acetate, oxalate, citrate and tartrate.
6. method according to claim 1 or 5, it is characterized in that: metal compound solution is mixed with mixed solution, in metal compound solution, with the group vib metal component content of oxide basis for 5.0 ~ 30.0g/100mL, group VIII metal constituent content 1.0 ~ 5.0gNiO/100mL.
7. method according to claim 1 or 5, is characterized in that: add adjuvant component in step (2), adjuvant component is the compound of one or more in P, F, B, Zr and Ti.
8. method according to claim 1, is characterized in that: in step (3), peptizing agent is acid solution, and acid solution is one or the mixed acid of formic acid, acetic acid, ethanedioic acid, citric acid and/or phosphoric acid.
9. method according to claim 2, is characterized in that: ammonia scrubbing adopt pH value be 8 ~ 14 ammoniacal liquor wash.
10. method according to claim 9, is characterized in that: during washing, ammonia volume is 1 ~ 3 times that waits to wash volume of material; Wash time is 5 ~ 90 minutes, is preferably 10 ~ 40 minutes.
The application of the hydrocracking catalyst that described in 11. claims 1 prepared by method in heavy distillate hydrocracking reaction.
12. application according to claim 11, is characterized in that: the operating condition of hydrocracking reaction is hydrogen dividing potential drop 3 ~ 20MPa, and reaction temperature is 320 ~ 420 DEG C, and during liquid, volume space velocity is 0.5 ~ 3h
-1, hydrogen to oil volume ratio is 500:1 ~ 3000:1.
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| CN1352231A (en) * | 2000-11-08 | 2002-06-05 | 中国石油化工股份有限公司 | Hydrogenating and pour point depressing catalyst and its preparing method |
| CN102284295A (en) * | 2010-06-21 | 2011-12-21 | 中国石油化工股份有限公司 | Dipping solution of hydrogenation catalyst and method for preparing hydrogenation catalyst |
| CN102310003A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN102309975A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for preparing hydrocracking catalyst |
| CN102794203A (en) * | 2011-05-23 | 2012-11-28 | 中国石油化工股份有限公司 | Special hydrocracking catalyst and preparation method and application thereof |
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