CN104646072A - Preparation method of hydrotreating catalyst carrier - Google Patents
Preparation method of hydrotreating catalyst carrier Download PDFInfo
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- CN104646072A CN104646072A CN201310584306.1A CN201310584306A CN104646072A CN 104646072 A CN104646072 A CN 104646072A CN 201310584306 A CN201310584306 A CN 201310584306A CN 104646072 A CN104646072 A CN 104646072A
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Abstract
The invention relates to a preparation method of a hydrotreating catalyst carrier. The preparation method includes following steps: (1) preparing a halogen inorganic acid solution; (2) mixing the halogen inorganic acid solution with an oxide precursor to obtain a binding agent; (3) mixing the binding agent with catalyst carrier raw material powders and performing a moulding and drying process; and (4) impregnating the dried material in the step (3) with an ammonia water solution, an ammonium carbonate solution or an ammonium bicarbonate solution, and drying and roasting the impregnated material to obtain the catalyst carrier. Compared with a preparation method in the prior art, the preparation method is carried out with the low-pollution and low-cost halogen inorganic acid as an acidic glue solvent during the process, so that a problem of NOx pollution during the preparation process of the catalyst carrier is solved and a poor influence on performances of the catalyst carrier with the halogen inorganic acid is overcome.
Description
Technical field
The present invention relates to a kind of supported catalyst agent carrier and preparation method thereof, especially in preparation process without NO
xthe carrier of hydrogenating catalyst preparation method of discharge.
Background technology
Along with crude quality becomes heavy year by year, is deteriorated, environmental regulation is increasingly strict, and the demand of market to clear gusoline constantly increases, and the hydrogen addition technology producing clean fuel is obtained and applies more and more widely.Under distillate hydrogenation process refers to HTHP, there is the saturated catalytic reaction of hydrodesulfurization, hydrodenitrogeneration, hydrogenation deoxidation, HDM and hydrogenation of unsaturated hydrocarbons in feedstock oil and hydrogen on catalyst surface.Because crude quality is deteriorated year by year, and refinery is for increasing economic efficiency, start generally to adopt crude oil deep vacuum distillation technology, doing of vacuum distillate is made to have brought up to more than 600 DEG C by original 520 DEG C, its density is increasing, boiling range is more and more higher, the molecular weight of contained hydrocarbon molecule is increasing, impurity content also gets more and more, especially sulfur-bearing, the baroque condensed-nuclei aromatics compounds content of nitrogen impurity increase greatly, the difficulty of deviating from of impurity increases greatly, and easily causes carbon deposit coking to reduce catalyst activity.Therefore, hydrotreated feed oil and product are all had higher requirement to hydrotreating techniques and hydrotreating catalyst.
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.Shaping of catalyst technology mainly comprises spray shaping, forming oil column, extruded moulding, compression molding and rotational forming etc.The fixed bed carried type hydrotreating catalyst of oil refining field of hydrogenation adopts extruded moulding method usually.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 the dry glue of oxide Homogeneous phase mixing according to a certain percentage, obtains jelly through stirring, ageing.
In catalyst or carrier extruded moulding process, adhesive adopts the mixing jelly of the oxide that acid stronger non-volatile inorganic is sour and pore volume is less usually, as CN93117528.3 adopts the inorganic oxide of aluminium oxide, titanium oxide, silica and clay or inorganic matter oxide mixture and inorganic acid to prepare adhesive.US8,021,540 adopt inorganic matter powdered components as shaping of catalyst adhesive, as clay, imvite, waterglass etc., and US7,687,676 directly use mineral acid acidified Ludox or Alumina gel as the adhesive in shaping of catalyst process.The effect of adhesive is that after the various component Homogeneous phase mixing by catalyst or carrier, peptization becomes the paste shape that can squeeze, and (banded extruder) carries out extruded moulding at elevated pressures, then carries out drying and high-temperature roasting process.In drying and roasting process, biochemical reaction is issued in the effect of strong acid and little orifice oxide between the contact interface of each component, form the staggered chemical bond be connected each other, thus make catalyst or carrier have certain geometric shape and very high withstand voltage, scuff resistance.Wherein the effect of little orifice oxide not easily interacts in catalyst or carrier between the larger component of pore volume, plays the effect of connection or grafting, make it combine closely each other, improve the mechanical strength of shaping rear catalyst or carrier.Therefore, the acids used as catalyst or carrier forming adhesive needs to have stronger acidity, and noresidue after decomposes; The little pore volume oxide used then needs to have less granularity and pore volume.
Nitric acid has acid strong, easy decomposition, price is low, and the advantage such as noresidue in the catalyst after decomposing, prepare the inorganic acid that hydrocracking catalyst the most often uses, and the maximum medium and small orifice oxide of adhesive of industrial application usually adopt adhesive property good, prepare easy γ-aperture aluminum oxide precursor thing.CN97121663.0 gives a kind of beta-zeolite molecular sieve catalyst and preparation method thereof, and the adhesive using the aluminum oxide precursor thing (boehmite) of nitric acid and little pore volume to prepare in the preparation process of catalyst, obtains good effect.But decomposes is discharged a large amount of NO by nitric acid in follow-up roasting process
x, causing suitable environmental hazard, is one of key factor of restriction Catalyst Production link.NO
xbeing a kind of main atmospheric pollutant, is form one of acid rain, photochemical fog and the primary pollution source causing ozone hole, the NO in waste gas
xmore difficultly remove, conventional method is more difficult by NO
xthoroughly remove.In addition, a large amount of NO
xgeneration also can cause heavy corrosion to production equipment and very big infringement be caused to operator ' s health.According to statistics, 1 ton of hydrogenation catalyst is often produced by generation about 45 standard cubic meter NOx.Flourish along with hydrogen addition technology, the use amount of hydrogenation catalyst is also in swift and violent increase, and this also causes the pollution problem of NOx and day to be aggravated, and the solution of this problem has been imperative.
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.Therefore, in shaping of catalyst process nitric acid alternative acids be selected to the problem that receives publicity.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 can the impurities left such as Cl, S, P be there is on a catalyst support in these inorganic acids, these impurity can affect the surface nature of catalyst carrier, the further serviceability affecting catalyst, therefore, these inorganic acids are not suitable as the peptizing agent of shaping of catalyst.
Summary of the invention
For the deficiencies in the prior art, the present invention adopts the halogen family inorganic acid of low stain in production process, low cost as sour peptizing agent, solves the NO of catalyst carrier production process
xthe deficiency that pollution problem and halogen family inorganic acid affect catalyst carrier serviceability.
The preparation process of catalyst carrier of the present invention comprises following content:
(1) halogen inorganic acid solution is prepared;
(2) above-mentioned halogen inorganic acid solution mixes with oxide precursor, prepares adhesive;
(3) adhesive of step (2) mixes with catalyst support material powder, then carries out shaping, dry;
(4) the dried material of step (3) adopts ammonia spirit, sal volatile or ammonium bicarbonate soln to carry out impregnation process, then carries out drying, roasting, obtains catalyst carrier.
In step of the present invention (1), halogen inorganic acid is one or more of hydrofluoric acid, hydrochloric acid, bromic acid and acid iodide, is preferably hydrochloric acid.The concentration of halogen inorganic acid solution is 0.2 ~ 2.6mol/L.
In step of the present invention (2), oxide precursor is that catalyst field prepares adhesive conventional substances, as one or more in aperture boehmite, aperture silica gel, aperture magnesium hydroxide, aperture contained amorphous silica-alumina dry glue etc.The granularity of above-mentioned substance requires to be less than 100 orders, is preferably less than 180 orders.In adhesive, the mol ratio of inorganic acid and oxide is 0.05 ~ 2.2, is preferably 0.15 ~ 1.6.Adhesive preparation method is well known to those skilled in the art, is specially inorganic acid solution and mixes with oxide precursor, and through stirring, ageing 2 ~ 12 hours, obtains adhesive.
In the inventive method step (3), catalyst carrier material is determined according to the specific requirement of Kaolinite Preparation of Catalyst, is generally one or more in aluminium oxide, silica, magnesia, titanium oxide, zirconia, amorphous aluminum silicide, molecular sieve, active carbon etc.Support material can be the precursor of above-mentioned carrier material or carrier material, and the selection of carrier material and support material is the Conventional wisdom of those skilled in the art.With remaining oxide basis, the weight percentage of adhesive in final catalyst carrier is 5.0% ~ 50.0%, is preferably 10.0% ~ 40.0%.In step (3), shaping and drying can adopt this area conventional method, dry general at 50 ~ 200 DEG C dry 2 ~ 48 hours.
In the inventive method step (4), the dried material of step (3) adopts ammonia spirit, sal volatile or ammonium bicarbonate soln to carry out in impregnation process process, and the concentration of solution is generally 0.5 ~ 6mol/L, is preferably 1 ~ 4mol/L.Solution usage is generally 30% ~ 200% of material water absorption rate, is preferably 50% ~ 100%.Drying in step (4) and roasting can adopt normal condition, dry general at 50 ~ 200 DEG C dry 2 ~ 48 hours, roasting generally roasting 2 ~ 10 hours at 350 ~ 950 DEG C.
The present invention is directed to the NOx pollution problem of catalyst preparation process, select the clean halogen family inorganic acid without ammonia nitrogen discharge as Aci-Jel solvent, then halogen family inorganic acid is solved on the impact of catalyst support surface performance by post-processing approach, have adjusted the surface nature of catalyst carrier, be conducive to the raising of this carrier Kaolinite Preparation of Catalyst serviceability.Meanwhile, eliminate the problem of nitrate anion pollution sources from source, the preparation process adopting extruded moulding catalyst and catalyst carrier can be widely used in.
The present invention have employed the halogen family inorganic acid close with nitric acid character, substantially can adopt original preparation technology's flow process, can prepare the carrier of hydrogenating catalyst of the high strength meeting various performance requirement.
Feature of the present invention is to adopt halogen family inorganic acid, after catalyst carrier shaping and drying, process with inorganic caustic solutions, before support material transforms, carry out suitable treatment, be conducive to regulating carrier surface character, eliminate halogen family inorganic acid to the impact of catalyst performance.
Preparation method of the present invention is simple, be easy to operation, the prices of raw and semifnished materials are low, can economy, environmental protection, prepare the preparation process being suitable for various extruded moulding catalyst or carrier efficiently, special-less process requirement, utilizes on existing equipment and just can realize whole production.
Detailed description of the invention
In the inventive method, by modified catalyst supports component as macroporous aluminium oxide powder and/or contained amorphous silica-alumina dry glue powder, and other auxiliary agent, after the mixture such as expanding agent, lubricant is fully dry mixed, add adhesive and carry out shaping, extrusion, banded extruder orifice plate can be cylindrical, clover, bunge bedstraw herb or other abnormity, then carries out low temperature drying, high-temperature roasting activates, and prepares the carrier of hydrogenating catalyst of high strength.
Below by the preparation process of carrier of hydrogenating catalyst, further illustrate Method and Process of the present invention:
1) ~ 0.5mol/L halogen family inorganic acid solution is made.
2) the little porous aluminum oxide 720g that butt (weight) is 72.2% is taken.Little porous aluminum oxide is that commercially available Alchlor process prepares aperture boehmite, pore volume 0.32mL/g, specific area 286m
2/ g, granularity is less than 180 orders.
3) the halogen family inorganic acid solution 1265mL measured in step 1 slowly joins in the mortar placing little porous aluminum oxide, after static 20min, stir, become white translucent paste shape, standing at room temperature ageing 8h, prepares this catalyst carrier and uses adhesive.
4) catalyst carrier key component macroporous aluminium oxide or contained amorphous silica-alumina dry glue product pulverized, granularity of sieving is less than 180 orders, according under the constant temperature condition of 3 hours at 600 DEG C, do each component in catalyst carrier butt composition.
5) get modified aluminas and contained amorphous silica-alumina dry glue powder in proportion, add extrusion aid or its auxiliary agent, auxiliary agent can be containing one or more of F, B, P, Zr and Ni compound, then carries out kneading, makes it fully mix.
6) powder mixture being added adhesive carries out shaping, extrusion, dry.Adopt ammonia spirit, sal volatile or ammonium bicarbonate soln to carry out impregnation process after drying, then carry out drying, roasting, obtain catalyst carrier.Forming method is extruded moulding, and banded extruder orifice plate can be cylindrical, clover, bunge bedstraw herb or other abnormity.
Carrier of hydrogenating catalyst of the present invention has following character, and shape is bar shaped, cylindric, clover, bunge bedstraw herb, tooth ball or other irregular strip; Diameter 1.0 ~ 6.0mm, preferably 1.2 ~ 3.0mm, crushing strength 140 ~ 280N/cm, preferably 160 ~ 240N/cm; Abrasion resistance 0 ~ 2%; Specific area 240 ~ 600m
2/ g, preferably 300 ~ 480m
2/ g; Pore volume 0.30 ~ 1.00cm
3/ g, preferably 0.40 ~ 0.80cm
3/ g; Bulk density 0.40 ~ 0.80g/cm
3, preferably 0.50 ~ 0.70g/cm
3.
Example 1(referencing schemes)
Get 1280mL dilute nitric acid solution (concentration is 4g nitric acid/100mL), add 720g aperture boehmite (Germany produces SB powder) gradually, after static 20min, stir, become white translucent paste shape, standing at room temperature ageing 8h, prepares adhesive.(Tianjin is cut Noya Inc. and is produced, pore volume 0.80mL/g, specific area 295m to get 580g macroporous aluminium oxide
2/ g, butt 72.1%), add 6g sesbania powder, and add 562.9g adhesive, roll 30 minutes, add appropriate distilled water, make mixture become can squeeze paste shape, extrusion, banded extruder orifice plate diameter is 1.5mm clover.Wet bar at 120 DEG C dry 4 hours, then carries out roasting, temperature 550 DEG C, 3 hours time, numbering HT-1S.
Example 2(referencing schemes)
Example 1 dilute nitric acid solution is changed to acetic acid solution (concentration is 13.2g acetic acid/100mL), other, with example 1, prepares carrier, numbering HT-2S.
Example 3(referencing schemes)
Example 1 dilute nitric acid solution is changed to citric acid solution (concentration is 18.8g citric acid/100mL), other, with example 1, prepares carrier, numbering HT-3S.
Example 4(referencing schemes)
Example 1 dilute nitric acid solution is changed to HF acid solution (concentration is 1.25gHF/100mL), other, with example 1, prepares carrier, numbering HT-4S.
Example 5(scheme of the invention)
Example 1 dilute nitric acid solution is changed to dilute hydrochloric acid solution (concentration is 2.2g hydrochloric acid/100mL), other, with example 1, prepares carrier, numbering HT-5S.
Example 6(scheme of the invention)
Example 1 dilute nitric acid solution is changed to HF acid solution (concentration is 1.25gHF/100mL), after shaping and drying, material working concentration is that the ammoniacal liquor of 2mol/L carries out impregnation process, ammonia volume is 100% of dry rear material water absorption rate, and then carry out drying and roasting, wherein drying is at 160 DEG C dry 4 hours, roasting roasting 3 hours at 450 DEG C.Other, with example 1, prepares carrier, numbering HT-6S.
Example 7(scheme of the invention)
Example 1 dilute nitric acid solution is changed to dilute hydrochloric acid solution (concentration is 2.2g hydrochloric acid/100mL), after shaping and drying, material working concentration is that the ammonium bicarbonate soln of 3mol/L carries out impregnation process, solution usage is 120% of dry rear material water absorption rate, and then carry out drying and roasting, wherein drying is at 140 DEG C dry 6 hours, roasting roasting 2 hours at 490 DEG C.Other, with example 1, prepares carrier, numbering HT-7S.
Example 8(alternative)
By example 7 scheme, just ammonium bicarbonate soln carries out carrying out after impregnation process step is arranged on catalyst roasting, and dry again and roasting 1 hour at 400 DEG C after dipping ammonium bicarbonate soln, prepares carrier, numbering HT-8S.
Carrier HT-1S ~ HT-5S and HT-8S is comparison example, and HT-6S ~ HT-7S is example of the present invention, and physico-chemical property lists in table 1.Carrier HT-5S, HT-S7 and HT-8S are impregnated in molybdenum nickel phosphorus solution and carry out supersaturation dipping, then 500 DEG C of roasting 3h, are numbered HT-5, HT-7, HT-8.Catalyst physico-chemical property is in table 2.
The physico-chemical property of table 1. carrier
| Numbering | HT-1S | HT-2S | HT-3S | HT-4S | HT-5S | HT-6S | HT-7S | HT-8S |
| Heap ratio, g/mL | 0.602 | 0.589 | 0.599 | 0.621 | 0.617 | 0.615 | 0.612 | 0.613 |
| Crushing strength, N/cm | 210 | 126 | 117 | 211 | 224 | 212 | 227 | 218 |
| Abrasion resistance, wt% | 0.8 | 1.4 | 1.9 | 0.7 | 0.5 | 0.2 | 0.3 | 0.3 |
| S BET，m 2/g | 324 | 335 | 344 | 327 | 316 | 331 | 341 | 332 |
| V SIN，mL/g | 0.612 | 0.620 | 0.628 | 0.601 | 0.589 | 0.625 | 0.631 | 0.630 |
| R BET，nm | 7.4 | 8.2 | 8.0 | 7.5 | 7.3 | 7.8 | 8.1 | 8.2 |
The physico-chemical property of table 2. catalyst
| Numbering | HT-5 | HT-7 | HT-8 |
| Chemical composition, wt% | |||
| MoO 3 | 23.4 | 22.6 | 22.5 |
| NiO | 3.8 | 4.1 | 4.1 |
| Al 2O 3 | Surplus | Surplus | Surplus |
| P 2O 5 | 1.1 | 0.9 | 0.9 |
| Physico-chemical property | |||
| Heap ratio, g/mL | 0.841 | 0.845 | 0.844 |
| Crushing strength, N/cm | 212 | 214 | 213 |
| Abrasion resistance, wt% | 0.6 | 0.4 | 0.4 |
| S BET，m 2/g | 198 | 187 | 188 |
| V SIN，mL/g | 0.341 | 0.334 | 0.336 |
R
bETfor the average pore diameter that BET method records.
Strength detection, ZQJ-II Intelligent testing machine for particle.
Catalyst HT-5, catalyst HT-7, catalyst HT-8 apply in aromatic hydrogenation saturated reaction, and catalyst carries out conventional vulcanizing treatment before using.With cycloalkyl straight run kerosene fraction for raw material (smoke point 18), reaction condition is hydrogen dividing potential drop 2MPa, reaction temperature 260 DEG C, and hydrogen to oil volume ratio is 200:1, and during material liquid, volume space velocity is 4h
-1.After catalyst HT-5 process, the smoke point of product is 25, and after catalyst HT-7 process, the smoke point of product is 28, and after catalyst HT-8 process, the smoke point of product is 25.
Claims (10)
1. a preparation method for catalyst carrier, is characterized in that comprising following content:
(1) halogen inorganic acid solution is prepared;
(2) above-mentioned halogen inorganic acid solution mixes with oxide precursor, prepares adhesive;
(3) adhesive of step (2) mixes with catalyst support material powder, then carries out shaping, dry;
(4) the dried material of step (3) adopts ammonia spirit, sal volatile or ammonium bicarbonate soln to carry out impregnation process, then carries out drying, roasting, obtains catalyst carrier.
2. method according to claim 1, is characterized in that: in step (1), and halogen inorganic acid is one or more of hydrofluoric acid, hydrochloric acid, bromic acid and acid iodide, is preferably hydrochloric acid.
3. method according to claim 1 and 2, is characterized in that: in step (1), and the concentration of halogen inorganic acid solution is 0.2 ~ 2.6mol/L.
4. method according to claim 1, is characterized in that: in step (2), and oxide precursor is one or more in aperture boehmite, aperture silica gel, aperture magnesium hydroxide, aperture contained amorphous silica-alumina dry glue.
5. method according to claim 4, is characterized in that: in step (2), and the granularity of oxide precursor is less than 100 orders, is preferably less than 180 orders.
6. method according to claim 1, is characterized in that: in step (2), and the mol ratio of inorganic acid and oxide is 0.05 ~ 2.2, is preferably 0.15 ~ 1.6.
7. method according to claim 1, is characterized in that: in step (3), with oxide basis, and the weight percentage of adhesive meter in final catalyst carrier is 5.0% ~ 50.0%, is preferably 10% ~ 40%.
8. method according to claim 1, it is characterized in that: in step (4), the dried material of step (3) adopts ammonia spirit, sal volatile or ammonium bicarbonate soln to carry out in impregnation process process, and the concentration of solution is 0.5 ~ 6mol/L, is preferably 1 ~ 4mol/L.
9. the method according to claim 1 or 8, is characterized in that: in step (4), and solution usage is 30% ~ 200% of material water absorption rate, is preferably 50% ~ 100%.
10. method according to claim 1, is characterized in that: in step (4), dry at 50 ~ 200 DEG C dry 2 ~ 48 hours, roasting roasting 2 ~ 10 hours at 350 ~ 950 DEG C.
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Cited By (2)
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| CN110935461A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrodemetallization catalyst |
| CN110935462A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110935461A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrodemetallization catalyst |
| CN110935462A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN110935461B (en) * | 2018-09-25 | 2022-07-08 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrodemetallization catalyst |
| CN110935462B (en) * | 2018-09-25 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
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