CN104646071A - Clean preparation method of hydrotreating catalyst carrier - Google Patents
Clean preparation method of hydrotreating catalyst carrier Download PDFInfo
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- CN104646071A CN104646071A CN201310584275.XA CN201310584275A CN104646071A CN 104646071 A CN104646071 A CN 104646071A CN 201310584275 A CN201310584275 A CN 201310584275A CN 104646071 A CN104646071 A CN 104646071A
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Abstract
The invention relates to a clean preparation method of a hydrotreating catalyst carrier. The clean preparation method includes following steps: preparing a mixed acid solution, in which phosphorus acid and an organic acid are contained; mixing the mixed acid solution with an oxide precursor to prepare a binding agent; mixing the binding agent with catalyst carrier raw material powders; and performing a moulding process, a drying process and a roasting process to obtain the hydrotreating catalyst carrier. Compared with the prior art, the invention provides the clean preparation method of the hydrotreating catalyst carrier, by which a problem of polluting exhaust gas emission during the preparation process of the catalyst carrier is solved by employing the composite acid, and meanwhile performances of the catalyst carrier are ensured.
Description
Technical field
The present invention relates to a kind of preparation method of supported catalyst agent carrier, especially in preparation process without NO
xthe preparation method of the carrier of hydrogenating catalyst 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 catalytic reactions such as hydrodesulfurization, hydrodenitrogeneration, hydrogenation deoxidation, HDM and hydrogenation of unsaturated hydrocarbons are saturated 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 material impact to fluid resistance, air velocity, the distribution of bed temperature gradient, concentration gradient distribution etc.In order to give full play to the catalytic performance of catalyst, 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 calcination 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 is between the component that not easily interactional pore volume is larger in catalyst or carrier, plays the effect of connection or grafting, makes 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 after decomposes noresidue impurity; 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 hydrogenation 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, cause suitable environmental hazard, NO
xbe the pollutant type of very difficult purified treatment, become 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.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, often produce 1 ton of hydrogenation catalyst by generation about 45 standard cubic meter NOx, these NOx are dispersed in Catalyst Production tail gas with low concentration, define a large amount of difficult emission of volume.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 the raw material of some clean nitrogenfree oxide discharges 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 except nitric acid, most of inorganic acid, as all there is impurities left problem after the decomposes such as sulfuric acid, hydrochloric acid, hydrofluoric acid, needs to carry out post processing, be not suitable for directly as the peptizing agent (or peptization acid) of shaping of catalyst.For organic acid, noresidue element after most decomposes, but acetic acid, citric acid and acetic acid etc. that wherein price is relatively low, acid on the weak side, peptization performance is not strong, is not suitable for separately as the peptizing agent of shaping of catalyst.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of catalyst support preparation method, by adopting Compound-acid, solving the problem of contaminative exhaust emissions in catalyst carrier production process, ensure that the serviceability of catalyst carrier simultaneously.
The preparation process of catalyst carrier of the present invention comprises following content:
(1) prepare mixed acid solution, containing phosphoric acid and organic acid in mixed acid solution, wherein the molar concentration of phosphoric acid is 0.1 ~ 3.0mol/L, and organic acid molar concentration is 0.2 ~ 5.0mol/L;
(2) above-mentioned mixed acid solution mixes with oxide precursor, prepares adhesive;
(3) adhesive of step (2) mixes with catalyst support material powder, then carries out shaping, dry, roasting, obtains catalyst carrier.
In the inventive method, the organic acid described in step (1) be formic acid, acetic acid, ethanedioic acid, citric acid, acetic acid one or more.In mixed acid solution, the mol ratio of organic acid and phosphoric acid is 0.1:1 ~ 10.0:1.First prepare organic acid soln, will add appropriate deionized water in organic acid, heating promotes to dissolve, and then lowers the temperature, adds appropriate concentrated phosphoric acid, make mixed acid solution in organic acid.
In the inventive method, in step (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 total acid and oxide is 0.05:1 ~ 3.0:1, is preferably 0.05:1 ~ 1.8:1.Adhesive preparation method is well known to those skilled in the art, is specially mixed acid solution and mixes with oxide precursor, stir, and ageing 2 ~ 12 hours, obtains adhesive.
In the inventive method, in step (3), catalyst support component 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 component itself or carrier component, and the selection of carrier material and support material is the Conventional wisdom of those skilled in the art.With oxide basis, the weight percentage of adhesive in final catalyst carrier is 3.0% ~ 45.0%, is preferably 7.0% ~ 35.0%.In step (3), shaping, dry and roasting can adopt this area conventional method, dry general at 50 ~ 200 DEG C dry 2 ~ 48 hours, roasting generally roasting 2 ~ 10 hours at 350 ~ 950 DEG C.
The catalyst carrier shape that the inventive method obtains is bar shaped, cylindric, clover, bunge bedstraw herb, tooth ball or other irregular strip etc.; 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.Phosphorus content is 0.5% ~ 1.5%.
The present invention is directed to the NOx pollution problem of catalyst carrier production process, select the organic acid cleaning and remain without ammonia nitrogen discharge, free from admixture as Aci-Jel solvent, the introducing of nitrate anion pollution sources is eliminated from source, prepare organic acid and phosphoric acid mixed acid adhesive, the preparation process adopting extruded moulding catalyst and catalyst carrier can be widely used in.
Although it is residual in the catalyst also to generate phosphorus pentoxide after phosphoric acid decomposes, but P elements can be used as the adjuvant component of hydrogenation catalyst, to carrier surface, there is certain modification, prevent the generation of nickel aluminate, also has good cementation, be conducive to the preparation of hydrogenation catalyst and the performance of performance, be widely applied in hydrotreating catalyst.Therefore, phosphoric acid can use as peptizing agent as clean inorganic acids, but addition is subject to certain restrictions, and too much P elements remains the pore structure that can affect catalyst carrier.
When organic acid is for the preparation of adhesive, because acid strength is more weak, the catalyst carrier that intensity meets the demands cannot be obtained.Phosphoric acid belongs to middle strong acid, when only preparing adhesive with phosphoric acid, the catalyst that intensity meets the demands can not be obtained, and residual with due to P elements, the consumption of phosphoric acid is restricted, and the mode that therefore cannot be improved adhesive strength by the consumption improving phosphoric acid improves catalyst carrier intensity.The present invention is by research, shockingly find, coordinated with appropriate organic acid by a small amount of phosphoric acid, can ensure that residuals is lower on the one hand, meet the composition requirement of carrier, greatly can improve the intensity of carrier on the other hand, solve the problem using organic acid cannot prepare high strength catalyst carrier.
Preparation method of the present invention is simple, is easy to operation, can economy, environmental protection, prepare the preparation process being suitable for various extruded moulding catalyst or carrier efficiently, special-less process requirement, utilize on existing equipment and just can realize whole production.
Detailed description of the invention
The present invention adopts the peptizing agent of Compound-acid as catalyst of organic acid and phosphoric acid, adding of a small amount of phosphoric acid just can make up the acid weak deficiency of organic acid, the catalyst carrier that intensity meets the demands can be prepared, although P elements also exists the residual problem of element, a small amount of P elements can not bring negative impact to the performance of catalyst.
Below in conjunction with the preparation method of carrier of hydrogenating catalyst, illustrate the process of the inventive method:
(1) prepare organic acid soln, weigh 1320g oxalic acid (ethanedioic acid) white crystal, be dissolved in the distilled water of 50 DEG C of constant temperature stirrings, stir 20 minutes, add SPA 110mL, continue stirring and join 20min, make transparent 5000mL mixed acid solution.
(2) the little porous aluminum oxide 720g that butt 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, bulk density ~ 0.42g/cm
3, granularity is less than 180 orders.
(3) the mixed acid solution 1180mL measured in step 1 slowly joins in the mortar placing little porous aluminum oxide, after static 20min, stirs, and becomes 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, determines the butt composition of each component.
(5) modified aluminas and contained amorphous silica-alumina dry glue powder in proportion, adds extrusion aid or its auxiliary agent, and auxiliary agent can be containing one or more of F, B, Zr and Ni compound, then carries out kneading, makes it fully mix.
(6) powder mixture being added adhesive carries out shaping, and extrusion, then prepares carrier of hydrogenating catalyst.Its forming method is extruded moulding, and banded extruder orifice plate can be cylindrical, clover, bunge bedstraw herb or other abnormity, then carries out drying, roasting, prepares carrier of hydrogenating catalyst.
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 acetic acid solution (concentration is 26.4g acetic acid/100mL), other, with example 1, prepares carrier, numbering HT-4S-1.
Example 1 dilute nitric acid solution is changed to phosphoric acid solution (0.8g phosphoric acid/100mL), other, with example 1, prepares carrier, numbering HT-4S-2.
Example 5(scheme of the invention)
Example 1 dilute nitric acid solution is changed to acetic acid and phosphoric acid mixed solution (concentration is 13.2g acetic acid/100mL+0.8g phosphoric 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 acetic acid and phosphoric acid mixed solution (concentration is 13.2g acetic acid/100mL+1.5g phosphoric acid/100mL), other, with example 1, prepares carrier, numbering HT-6S.
Example 7(scheme of the invention)
Example 1 dilute nitric acid solution is changed citric acid and phosphoric acid mixed solution (concentration is 18.8g citric acid/100mL+1.5g phosphoric acid/100mL), other, with example 1, prepares carrier, numbering HT-6S.
Carrier HT-1S ~ 3S is comparison example, and HT-5S ~ 7S is example of the present invention, and physico-chemical property lists in table 1, and substantially pulverize after example 4 carrier calcination, intensity is very low.Be impregnated into by carrier HT-S1 and HT-S6 in molybdenum nickel phosphorus solution and carry out supersaturation dipping, then 500 DEG C of roasting 3h, are numbered HT-1 and HT-6.Catalyst physico-chemical property is in table 2.
The physico-chemical property of table 1. carrier
| Numbering | HT-1S | HT-2S | HT-3S | HT-5S | HT-6S | HT-7S |
| Chemical composition, % | ||||||
| P 2O 5 | -- | -- | -- | 0.91 | 1.52 | 1.55 |
| Physico-chemical property | ||||||
| Heap ratio, g/mL | 0.602 | 0.589 | 0.599 | 0.608 | 0.611 | 0.612 |
| Crushing strength, N/cm | 210 | 126 | 117 | 157 | 197 | 181 |
| Abrasion resistance, wt% | 0.8 | 1.4 | 1.9 | 1.1 | 0.9 | 0.7 |
| S BET，m 2/g | 324 | 335 | 344 | 347 | 315 | 362 |
| V SIN，mL/g | 0.612 | 0.620 | 0.628 | 0.631 | 0.620 | 0.624 |
| R BET，nm | 7.4 | 8.2 | 8.0 | 8.8 | 8.4 | 8.6 |
| Total acid content, Mmol/g | 0.41 | 0.38 | 0.56 | 0.57 | 0.54 | 0.64 |
R
bETfor the average pore diameter that BET method records.
Strength detection, ZQJ-II Intelligent testing machine for particle.
The physico-chemical property of table 2. catalyst
| Numbering | HT-1 | HT-6 |
| Chemical composition, % | ||
| MoO 3 | 23.4 | 22.6 |
| NiO | 3.8 | 3.4 |
| Al 2O 3 | 71.7 | 71.3 |
| P 2O 5 | 1.1 | 2.7 |
| Physico-chemical property | ||
| Heap ratio, g/mL | 0.841 | 0.856 |
| Crushing strength, N/cm | 212 | 204 |
| Abrasion resistance, wt% | 0.6 | 0.8 |
| S BET，m 2/g | 198 | 204 |
| V SIN，mL/g | 0.341 | 0.356 |
As can be seen from embodiment data, in the inventive method, place a small amount of phosphoric acid in organic acid soln, the adhesive of preparation may be used for preparation high strength catalyst carrier, without harmful tailpipe emissions in production process.
Claims (11)
1. a preparation method for catalyst carrier, is characterized in that comprising following process:
Preparation mixed acid solution, containing phosphoric acid and organic acid in mixed acid solution, wherein the molar concentration of phosphoric acid is 0.1 ~ 3.0mol/L, and organic acid molar concentration is 0.2 ~ 5.0mol/L;
Above-mentioned mixed acid solution mixes with oxide precursor, prepares adhesive;
The adhesive of step (2) mixes with catalyst support material powder, then carries out shaping, dry, roasting, obtains catalyst carrier.
2. method according to claim 1, is characterized in that: the organic acid described in step (1) be formic acid, acetic acid, ethanedioic acid, citric acid, acetic acid one or more.
3. method according to claim 1 and 2, is characterized in that: in step (1) mixed acid solution, and the mol ratio of organic acid and phosphoric acid is 0.1 ~ 10.0.
4. method according to claim 1, is characterized in that: in step (2), oxide precursor is that catalyst field prepares adhesive conventional substances.
5. the method according to claim 1 or 4, is characterized in that: in step (2), oxide precursor is one or more in aperture boehmite, aperture silica gel, aperture magnesium hydroxide, aperture contained amorphous silica-alumina dry glue.
6. the method according to claim 1 or 4, is characterized in that: the granularity of oxide precursor is less than 100 orders, is preferably less than 180 orders.
7. method according to claim 1, is characterized in that: in adhesive, the mol ratio of total acid and oxide is 0.05 ~ 3.0, is preferably 0.05 ~ 1.8.
8. method according to claim 1, is characterized in that: catalyst support component is one or more in aluminium oxide, silica, magnesia, titanium oxide, zirconia, amorphous aluminum silicide, molecular sieve, active carbon.
9. the method according to claim 1 or 8, is characterized in that: support material is carrier component itself or or the precursor of carrier component.
10. method according to claim 1, is characterized in that: with remaining oxide basis, and the weight percentage of adhesive in final catalyst carrier is 3.0% ~ 45.0%, is preferably 7.0% ~ 35.0%.
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 350 ~ 950 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112119052A (en) * | 2018-04-23 | 2020-12-22 | 科学设计有限公司 | Porous bodies with enhanced pore structure made with oxalic acid |
| CN113731385A (en) * | 2021-08-20 | 2021-12-03 | 宜昌苏鹏科技有限公司 | Catalyst carrier for preparing hydrogen peroxide by fixed bed anthraquinone process and preparation method of catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101322949B (en) * | 2008-07-18 | 2010-11-10 | 山西大学 | Alumina supporter and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112119052A (en) * | 2018-04-23 | 2020-12-22 | 科学设计有限公司 | Porous bodies with enhanced pore structure made with oxalic acid |
| CN113731385A (en) * | 2021-08-20 | 2021-12-03 | 宜昌苏鹏科技有限公司 | Catalyst carrier for preparing hydrogen peroxide by fixed bed anthraquinone process and preparation method of catalyst |
| CN113731385B (en) * | 2021-08-20 | 2023-11-28 | 宜昌苏鹏科技有限公司 | Catalyst carrier for preparing hydrogen peroxide by fixed bed anthraquinone method and preparation method of catalyst |
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