CN101081366A - Pd radicel duplex metal selective hydrogenation catalyzer and method for preparing the same and application thereof - Google Patents
Pd radicel duplex metal selective hydrogenation catalyzer and method for preparing the same and application thereof Download PDFInfo
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Abstract
The palladium-base bimetal catalyst for selective hydrogenation includes active zinc oxide as carrier; metal palladium as the active component in 0.03-0.3 wt% of the catalyst; and one of Cr, Ag, Ni, Cs and Pb as cocatalyst in 0.4-1.2 wt%. Its preparation process includes the steps of: roasting dried active zinc oxide carrier, soaking the carrier in palladium chloride solution with palladium content of 0.08-0.1 % and chromium trioxide with chromium content of 0.7-0.9 %, drying, roasting and pre-reducing. The catalyst has high activity, high selectivity, high stability, long service life and high catalytic efficiency.
Description
Technical field
The present invention relates to selective hydrocatalyst and preparation method thereof, and relate to a kind of method of using these catalyst to carry out selective hydrogenation; Particularly a kind of bimetallic selectively hydrogenating butadiene Catalysts and its preparation method and the method for carrying out selective hydrogenation.
Background technology
Oil processing unit can produce a large amount of C in process of production
4Hydrocarbon, this C
4Hydrocarbon mainly is made up of isobutene, 1-butylene, suitable-the 2-butylene, anti--the 2-butylene, normal butane, iso-butane etc., is very useful industrial chemicals, can be used to make multiple chemical products.Present domestic this C
4The hydrocarbon overwhelming majority is used as fuel burns, and is not used appropriately.Along with town gas and natural gas are popularized as the quick of domestic fuel, increasing C
4Hydrocarbon will be used as industrial chemicals, this shows, rationally utilize C
4The hydrocarbon resource has crucial economic implications and social effect.With regard to catalytic cracking process, C in the product
4The hydrocarbon amount can account for about 10% of raw material, and it is integrated to implement oil refining one chemical industry, carries out comprehensive utilization of resources, can effectively increase economic efficiency, and prospect is very considerable.
Above-mentioned C
4Also contain a small amount of alkadienes in the hydrocarbon, be generally 0.2%-2.0% (v).Scientific experimentation and industrial practice show that the secondary face of the existence of alkadienes rings C
4Some deep-processing process and the deep processed product of hydrocarbon, for example, in alkylated reaction, butadiene can generate the heavy applications as laminates, and it is the very high thickness mink cell focus of a kind of relative molecular mass, can make the rising of doing of alkylate oil, and octane number descends, and acid consumption simultaneously increases; As one of comonomer of producing LLDPE (LLDPE), the demand of 1-butylene increases by a fairly big margin recent years, yet the existence of butadiene but makes the 1-butylene not reach the quality requirement of comonomer; C
4The few butadiene that contains in the material of raffinate after etherificate is polymerization formation colloid on the etherificate resin easily, and the blocking catalyst duct reduces catalyst life.Therefore, this part butadiene is objectionable impurities in the process behind alkene, need in time remove.
The industrial method of extracting rectifying or selection hydrogenation of mainly taking removes C
4Butadiene in the cut.In recent years, multiple factor has caused extraction device two collection part energy consumptions to rise, and loss of material increases, and causes the process economy benefit relatively poor.Select hydrogen addition technology through constantly improving, possessed the incomparable advantage of extraction and distillation technology, not only butadiene can be removed, make the purity of gas alkene reach the requirement of further processing and utilization, can increase simultaneously the output of monoolefine, be most economical and the most received present method, become the first-selection that removes butadiene in the nature of things.
Normally used this selection hydrogenation catalyst contains noble metal as active component, Metal Palladium (being called for short Pd) is with its good catalytic hydrogenation activity and selectivity, be acknowledged as outstanding acetylene bond and diene key and select the activity of hydrocatalyst component, so the main active component of the various selective hydrogenation of butadiene catalyst of commercial Application is Pd at present, minority is also used Pt and Ni.But traditional selective hydrocatalyst active component adopts the monometallic palladium, and makes the catalyst of active component at C with the monometallic palladium
4Can produce some problems in the selection hydrogenation process of cut.As because combining of alkynes and diolefin and metal Pd causes Pd to be dissolved out from catalyst carrier, cause Pd to run off, cause the catalyst life shortening.Monometallic Pd catalyst hydrogenation activity is not high in addition, and selectivity is not good yet, has directly influenced the catalytic efficiency of butadiene, makes that the loss amount of butadiene is bigger, and cost is also higher.
Normally used this selection hydrogenation catalyst with noble metal loading on catalyst carrier, catalyst carrier has not only played load and has disperseed the effect of noble metal, raising precious metal catalyst efficient, reduction catalyst cost, and usually jointly catalytic reaction is had an effect with the catalyst activity component, so the selection of carrier is very important.Carrier is porous inorganic oxide normally, for example alundum (Al, silica, titanium dioxide etc.
Summary of the invention
Technical problem to be solved by this invention is at catalyst activity in the prior art and selectivity is not high, catalytic efficiency is low deficiency, a kind of catalyst and its preparation method are provided, its carrier and help catalyst component to be used makes activity of such catalysts and selectivity height, good stability, long service life, catalytic efficiency improve greatly.
For this reason, the invention provides a kind of Pd radicel duplex metal selective hydrogenation catalyzer, wherein, this catalyst is carrier with the activated zinc oxide, is benchmark with the gross mass of catalyst, in mass content, comprise following component: active component is a palladium metal, and its content is 0.03%-0.3%; Cocatalyst component is a kind of in chromium metal, silver metal, nickel metal, caesium metal or the lead metal, and its content is 0.4%-1.2%.
The present invention also provides a kind of Preparation of catalysts method, wherein, comprises the steps:
The present invention provides a kind of method of using above-mentioned catalyst to carry out selective hydrogenation again, and wherein, this method is to carry out in gas phase, its reaction temperature is 90-170 ℃, reaction pressure is 0.3-0.5MPa, and the ratio of hydrogen/butadiene amount of substance is 1.0: 1 to 5.0: 1, and the gas air speed is 500-2000h
-1
The present invention is carrier with the activated zinc oxide, and palladium metal is its active component.The content of palladium metal is too high to be caused deep hydrogenation easily and is unfavorable for industrialization, and content is too low to cause catalyst activity bad, and test shows that palladium metal content is proper between 0.08%-0.10% (mass fraction); Increased again and helped catalyst component chromium metal etc., can change the electronic structure of palladium metal, thereby improved the catalyst hydrogenation selectivity, evidence, the good catalytic activity that adds the chromium metal, the content of chromium metal is relatively good between 0.7%-0.9%, and the butylene selectivity can reach 100% in the product gas behind the hydrogenation, effectively balance activity of such catalysts and selectivity.
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Description of drawings
What Fig. 1 reflected is the influence of palladium metal content to catalyst performance;
What Fig. 2 reflected is the influence of chromium metal modification amount to catalyst performance;
What Fig. 3 reflected is preparation method's of the present invention flow chart;
What Fig. 4 reflected is the influence of temperature to the catalyst hydrogenation reaction;
What Fig. 5 reflected is the influence of the comparison catalytic hydrogenation reaction of hydrogen/butadiene amount of substance;
What Fig. 6 reflected is the influence of gas air speed to the catalyst hydrogenation reaction;
What Fig. 7 reflected is catalyst stability result of the test of the present invention.
The specific embodiment
The carrier of catalyst of the present invention is an activated zinc oxide, is benchmark with the gross mass of catalyst, and in mass content, comprise following component: active component is a palladium metal, and its content is 0.03%-0.3%; Helping catalyst component is a kind of in chromium metal, silver metal, nickel metal, caesium metal or the lead metal, and its content is 0.4%-1.2%.What Fig. 1 reflected is the influence of palladium metal content to catalyst performance.As can be seen from Figure 1, along with the increase of palladium metal content, increase the catalyst activity position, and catalyst activity increases, but palladium metal content is increased to a certain degree, and it is too active that catalyst seems, causes purpose product butylene deep hydrogenation easily, and selectivity descends; In addition, palladium metal content is too high, has increased the cost of catalyst, also can have a negative impact to the commercial Application of catalyst.The general palladium metal content of selecting is comparatively suitable between 0.08%-0.1% (mass fraction).
Be on the basis of main active component with palladium metal, adding respectively and help catalyst component, can be respectively a kind of in chromium metal, silver metal, nickel metal, caesium metal or the lead metal, table 1 for add different help catalyst component after, to the situation that influences of catalyst performance.
Table 1 helps the influence of catalyst component to catalyst performance
| Catalyst | Reaction temperature (℃) | Butadiene conversion (%) | Butylene selectivity (%) |
| Pd/ZnO | 130 | 98.9 | 85.2 |
| Pd-Ag/ZnO | 130 | 34.4 | 79.3 |
| Pd-Ni/ZnO | 130 | 93.0 | 72.5 |
| Pd-Ce/ZnO | 130 | 69.3 | 82.4 |
| Pd-Pb/ZnO | 130 | 54.4 | 93.1 |
| Pd-Cr/ZnO | 130 | 92.4 | 100 |
As can be seen from Table 1, after adding helped catalyst component chromium metal, catalyst selectivity had reached 100%, improves a lot than monometallic palladium metal catalyst, and its performance is better than other several metals.
Butadiene conversion and butylene selectivity are calculated by following formula respectively in the present invention:
What Fig. 2 reflected is the influence of chromium metal modification amount to catalyst performance.From the evaluation result of Fig. 2 as can be known, increase along with chromium metal modification amount, the butylene selectivity rises gradually, in chromium metal modification amount is 0.8% o'clock, the butylene selectivity has reached 100%, thereafter remain on this level always, be approximately at 0.9% o'clock in chromium metal modification amount, butadiene conversion begins to descend.In sum, when chromium metal modification amount was 0.7%-0.9%, butadiene conversion remained on 99%, and selectivity reaches more than 90%, is the best modification amount.
Table 2 is the influence of sintering temperature to the carrier rerum natura.Table 3 is the influence that sintering temperature distributes to carrier aperture.
Table 2 sintering temperature is to the influence of carrier rerum natura
| The carrier sintering temperature (℃) | Total pore volume (mLg -1) | Specific area (m 2·g -1) | Average pore size (nm) | Most probable aperture (nm) |
| 400 | 0.4335 | 45.7736 | 18.9 | 27.4 |
| 500 | 0.4475 | 38.8755 | 23.0 | 27.4 |
| 600 | 0.3758 | 28.7354 | 26.2 | 27.4 |
| 700 | 0.2429 | 16.8166 | 28.9 | 27.4 |
| 900 | 0.3005 | 12.6573 | 47.5 | 196 |
The influence that table 3 sintering temperature distributes to carrier aperture
| Sintering temperature (℃) | Pore-size distribution/% | |||||
| 3-10nm | 10-20nm | 20-30nm | 30-40nm | 40-50nm | ＞50nm | |
| 400 | 9.8 | 20.9 | 34.3 | 21.1 | 4.3 | 9.6 |
| 500 | 7.9 | 7.5 | 34.8 | 29.7 | 6.7 | 13.4 |
| 600 | 6.3 | 10.3 | 29.6 | 16.2 | 10.6 | 27.0 |
| 700 | 5.0 | 1.8 | 31.2 | 34.1 | 15.7 | 12.2 |
| 900 | 8.0 | 1.0 | 0.4 | 0.6 | 0.9 | 89.1 |
As known from Table 2, along with the raising of sintering temperature, the specific area of ZnO carrier reduces gradually, and average pore size increases gradually.Table 3 also demonstrates the raising along with sintering temperature, pore-size distribution trends towards bigger hole, especially through the carrier of 900 ℃ of roastings, mesopore seldom and has accounted for 89.1% greater than the macropore of 50nm, and the most probable aperture also increases to 196nm suddenly from 27.4nm, show that the sintering temperature of this moment has reached the fusing point of some component in the carrier, the part carrier has been in molten condition, so mesopore seldom, most holes have become macropore.Based on above characterization result, it is more appropriate that the catalyst carrier sintering temperature is controlled at 400 ℃-600 ℃.
Fig. 3 is preparation method's of the present invention flow chart.Present embodiment is a kind of above-mentioned Preparation of catalysts method, comprises the steps:
Present embodiment is a kind of method that above-mentioned catalyst carries out selective hydrogenation of using, this method is to carry out in gas phase, and its reaction temperature is 90-170 ℃, and reaction pressure is 0.3-0.5MPa, the ratio of hydrogen/butadiene amount of substance is 1.0: 1 to 5.0: 1, and the gas air speed is 500-2000h
-1
Carry out owing to being reflected under the gas phase condition, as long as pressure falls variation not quite before and after guaranteeing reactor, and guarantee the normal gasification rate of liquefied gas, the variation of pressure does not influence reacting basic, and reaction result is stablized constant.Consider that the pressure of liquid gas storage tank own is not high, and liquefied gas belongs to gradually gasification, pressure remains between the 0.3-0.5MPa proper when therefore reacting.
Fig. 4 is the influence of temperature to the catalyst hydrogenation reaction.From the evaluating catalyst result of Fig. 4 as can be known, along with the rising of reaction temperature, catalyst hydrogenation activity increases, and the content of remaining butadiene constantly reduces.But have to be noted that simultaneously high temperature easily facilitates polymerisation, cause the catalyst surface coking, the accelerator activator inactivation, so reaction temperature should be adjusted at and can keep activity of such catalysts, do not cause in the scope of the rapid coking of catalyst again.Result of the test shows that reaction temperature can be between 90-170 ℃, and the reaction optimum temperature range is 130-150 ℃.
Fig. 5 is the influence of the comparison catalytic hydrogenation reaction of hydrogen and butadiene amount of substance.By the evaluating catalyst result of Fig. 5 as can be known, along with the ratio of hydrogen/butadiene amount of substance improves, remaining butadiene content constantly reduces, and catalyst activity continues to raise, but the butylene loss is also in continuous increase, and catalyst selectivity descends; And the ratio of hydrogen/butadiene amount of substance is crossed when hanging down, and has reached 100% though hydrogenation generates the selectivity of butylene, and butadiene is hydrogenation and removing fully, and catalyst activity can't guarantee.Simultaneously according to result of the test, the conversion ratio of butadiene is to optionally influence is also very important, and for this phenomenon, most probable explanation is, covers the butadiene molecule number on the metal surface, can change along with the increase of conversion ratio.Butadiene has very strong bond to the Pd metal surface, therefore, only depresses at lower butadiene branch, and the 1-butylene just has an opportunity to be adsorbed onto the surface of Pd, and then carries out isomerization reaction.As shown in Figure 5, the ratio of hydrogen and butadiene amount of substance can be between 1.0: 1 to 5.0: 1, its optimised quantity than scope between 3.0: 1 to 4.0: 1.
Fig. 6 is the influence of gas air speed to the catalyst hydrogenation reaction.By the evaluating catalyst result of Fig. 6 as can be known, when the gas air speed was low, unstripped gas was longer in the beds time of staying, and hydrogenation reaction is carried out relatively fully, and remaining butadiene content is less relatively, but easily causes the excessive hydrogenation of butadiene, and the loss of butylene increases; When the gas air speed was higher, per volume of catalyst production capacity increased thereupon, and catalyst loading strengthens, but can shorten time of contact, and butadiene is difficult for by complete hydrogenation and removing, caused catalyst activity shortening in sexual cycle.In successive reaction, if whole conversion process has been controlled in mass transfer or heat transfer, then selectivity can reduce usually; literature research points out in the butadiene hydrogenation reaction, have external diffusion control to be present in beds; therefore, in order to improve selectivity, must careful selection gas air speed.As shown in Figure 6, the gas air speed can be 500-2000h
-1, at 900-1100h
-1Between the time activity of such catalysts and selectivity obtained balance well.
Table 4 is a catalyst basic physical properties parameter of the present invention.
Table 4 catalyst basic physical properties parameter
| Project | Data |
| Outward appearance | Taupe, bar shaped |
| Size (mm) | φ3×3-5 |
| Crushing strength (Ncm -1) | 109 |
| Specific area (m 2·g -1) | 38.88 |
| Bulk density (gmL -1) | 0.1927 |
| Pore volume (mLg -1) | 0.4475 |
| Average pore radius (nm) | 23.0 |
Fig. 7 is a catalyst stability result of the test of the present invention.Stability test is at the ratio 4.0 of 130 ℃ of reaction temperatures, inlet pressure 0.50MPa, outlet pressure 0.49MPa, hydrogen/butadiene amount of substance, gas air speed 1000h
-1Carry out down, fluctuate to some extent when activity of such catalysts has just begun under these process conditions, but butadiene conversion also all remains on more than 98%, heat release was more violent when the reason that this phenomenon occurs was to begin to react, cause the beds temperature rise higher, reached 8 ℃, after the reaction 7h, the catalyst operation begins to reply steadily, and catalyst activity is basicly stable about 99%; The butylene selectivity has also reached more than 98% substantially in the course of reaction, the deep hydrogenation phenomenon do not occur.The 12h operation result shows that the catalyst of development has possessed good hydrogenation activity and selectivity and good stable, has long service life, can satisfy industrialized demand substantially.
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not break away from the spirit and scope of technical solution of the present invention.
Claims (4)
1. a Pd radicel duplex metal selective hydrogenation catalyzer is characterized in that, this catalyst is carrier with the activated zinc oxide, gross mass with catalyst is a benchmark, in mass content, comprise following component: active component is a palladium metal, and its content is 0.03%-0.3%; Helping catalyst component is a kind of in chromium metal, silver metal, nickel metal, caesium metal or the lead metal, and its content is 0.4%-1.2%.
2. Pd radicel duplex metal selective hydrogenation catalyzer according to claim 1 is characterized in that, the described catalyst component that helps is the chromium metal, and its content is 0.7%-0.9%.
3. Pd radicel duplex metal selective hydrogenation catalyzer according to claim 1 is characterized in that, palladium metal content is 0.08%-0.10%, and the chromium tenor is 0.7%-0.9%.
4. the described Preparation of catalysts method of claim 1 is characterized in that, comprises the steps:
Step 1, get dried activated zinc oxide carrier, put into high temperature furnace and carry out roasting under 400-600 ℃, 200 ℃/hour of programming rates kept 3-4 hour after predefined temperature, reduced to room temperature then naturally, taking-up;
Step 2, be that the palladium chloride solution of 0.08%-0.1%, chromium trioxide solution that the chromium tenor is 0.7%-0.9% and the activated zinc oxide carrier after step 1 roasting soak altogether with palladium metal content;
Step 3, with after co-impregnated solution drying, roasting and the prereduction in the step 2, make catalyst.
5. method that application rights requires 1 described catalyst to carry out selective hydrogenation, it is characterized in that, this method is to carry out in gas phase, its reaction temperature is 90-170 ℃, reaction pressure is 0.3-0.5MPa, the ratio of hydrogen/butadiene amount of substance is 1.0: 1 to 5.0: 1, and the gas air speed is 500-2000h
-1
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| CN102205243A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Palladium-silver bimetallic hydrogenation catalyst |
| CN102211043A (en) * | 2011-04-07 | 2011-10-12 | 中国石油天然气股份有限公司 | Method for preparing palladium-silver bimetallic catalyst |
| CN101628843B (en) * | 2008-07-18 | 2013-11-27 | 环球油品公司 | Selective hydrogenation method utilizing layered catalyst composition and preparation of catalyst |
| CN103418378A (en) * | 2013-08-01 | 2013-12-04 | 济南开发区星火科学技术研究院 | Catalytic agent for cracking C-4 fraction selective hydrogenating palladium base |
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| CN102205243B (en) * | 2011-04-07 | 2013-02-13 | 中国石油天然气股份有限公司 | Palladium-silver bimetallic hydrogenation catalyst |
| CN102211043B (en) * | 2011-04-07 | 2013-04-24 | 中国石油天然气股份有限公司 | Method for preparing palladium-silver bimetallic catalyst |
| CN103418378A (en) * | 2013-08-01 | 2013-12-04 | 济南开发区星火科学技术研究院 | Catalytic agent for cracking C-4 fraction selective hydrogenating palladium base |
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