CN1295877A - Process for preparation of sulfur transfer catalyst - Google Patents
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Abstract
A preparation method of sulfur-transfer catalyst includes the following steps: soaking a kind of hydrated alumina microsphere in solution containing cerium compound, drying and roasting. The described hydrated alumina microphere is prepared by adopting a special method. The sulfur-transfer catalyst prepared by adopting the said method possesses higher abrasive resistance.
Description
The invention relates to a preparation method of a sulfur transfer catalyst containing alumina and cerium, in particular to a sulfur transfer catalyst containing alumina and cerium and used for reducing SO in regeneration flue gas in a catalytic cracking processXA method for preparing a sulfur transfer catalyst for pollutant emission.
In a Fluid Catalytic Cracking (FCC) process, the activity of the catalyst is reduced due to the deposition of coke on the catalyst as a result of the reaction of the hydrocarbons. Meanwhile, a part of sulfur in the feed oil is deposited on the catalyst together with coke. The cracked product is then withdrawn from the unit and the coke-containing catalyst is passed through a stripping section to remove hydrocarbons adsorbed on the catalyst before being passed to a regenerator. The coke-containing catalyst in the regenerator is contacted with air at high temperature and the coke on the catalyst is burned off, thereby restoring the activity of the catalyst. The catalyst after the activity is restored is conveyed to the reactor again, and the next reaction-regeneration cycle is started.
In the regenerator, CO and SO are generated when the catalyst is burntX、CO2. Usually these gases are discharged to the atmosphere, their CO, SOXWill cause pollution to the atmosphere.
Reducing the SO of the regenerated flue gas of fluid catalytic crackingXThere are many ways of venting. For example, methods for hydrodesulfurization of catalytic cracking feedstocks, methods for scrubbing of regenerated flue gas, methods forpurchasing low sulfur feedstocks, and methods for selecting SOXTransfer agent technology. Among them, the costs required for hydrogenation of raw materials and washing of flue gas are the highest, which not only costs a lot for construction of the plant, but also the source of raw materials is limited. Most notably the use of SO in several waysXThe transfer technology does not need to modify a catalytic cracking unit, and only needs to consume part of the catalyst cost. The process is easy to operate and can be used for reducing SO in an FCC unit without greatly changing the operating conditionsXThe purpose of discharging.
SOXThe transfer technology is that sulfur transfer catalyst (sulfur transfer agent for short) is added into the catalytic cracking device and physically mixed with the cracking catalyst, and the sulfur transfer agent and the catalytic cracking catalyst are circulated between the reactor and the regenerator. In the regenerator, the sulfur transfer agent and SO in the flue gasXReacting to form stable metal sulfate, attaching to the surface of the transfer agent, circulating to the reactor together with the regenerated cracking catalyst, reducing sulfur attached to the transfer agent in the form of metal salt in the reducing atmosphere of the reactor, and directly using H2The form of S is released. This part H2S and H formed by cracking reaction2The S is conveyed to a sulfur recovery device for recovery. The transfer agent after the sulfur removal in the reactor is regenerated and accompanied with the cracking catalystThe reagents are recycled together to the regenerator for the next SOxAnd (5) carrying out adsorption reaction. The chemical reaction of the transfer agent in the regenerator and reactor can be described simply as:
regenerator
Reactor with a reactor shell
Stripping section
Thus, the sulfur transfer agent functions such that it can remove SO from the regenerator3This requires that the sulfur transfer agent be effective in promoting SO in the regenerator2Formation of SO3. To achieve this reaction, the first investigators considered the best promoter to be the Pt catalyst. However, Pt is expensive. Therefore, a large number of researchers developed inexpensive and equivalent performance productsThe sulfur transfer agent of (1).
USP 5,021,228 discloses a method for removing a gaseous sulfur component from a sulfur oxide-containing mixed gas, which comprises contacting the sulfur oxide-containing mixed gas with a composition (sulfur transfer agent) comprising a porous carrier and 0.5 to 10% by weight of at least one actinide metal and 1 to 5% by weight of at least one alkali metal supported on the carrier at 800-. The preparation method of the composition comprises the steps of impregnating a carrier with an aqueous solution of a soluble compound of the metal, drying at the temperature of 300 ℃ F. (100 ℃ C.) (140 ℃ C.) for 1-24 hours, crushing, and roasting at the temperature of 1300 ℃ C.) (1500 ℃ C.) (704 ℃ C.) (816 ℃ C.). In the preferred embodiment of this patent, a thorium-containing sulfur transfer agent is used, which, although having very good sulfur transfer properties, is naturally occurring, Th232Is a radioactive substance and this sulfur transfer agent needs to be examined in many ways before use to ensure that the radioactive dose absorbed by the operator is below the required level, and therefore, the product is difficult to be widely used.
USP4,992,161 discloses a fluid catalytic cracking process which comprises circulating between the cracking zone and the regeneration zone a solid particulate comprising three separate components, (1) a particulate cracking catalyst comprising zeolite in the absence of hydrogen, (2) a particulate sulfur oxide adsorbent comprising an active alumina capable of adsorbing sulfur trioxide, (3) a particulate sulfur dioxide oxidation promoter comprising chromium and tin or an intimate combination of chromium and tin compounds supported on a titania support. The adsorbent is an independent component, and the accelerant adopts immersionBy impregnation, ion exchange or coprecipitation, etc., by supporting a chromium/tin compound on a carrier. This system has a very good oxidation promoting effect. However, chromium is a polyvalent element. Trivalent chromium is relatively less toxic, while hexavalent chromium is highly toxic and is a carcinogen. The chromium oxide used in the patent comprises CrO and Cr2O3And CrO3. The valency of which is divalent, trivalent and hexavalent. Thus, it is possible to provideHowever, its toxicity limits its widespread use in industrial production, despite its high activity.
USP4,642,177 discloses a catalytic cracking process comprising circulating a particulate cracking catalyst and a sulfur sorbent between a cracking reaction zone wherein said catalyst particles catalyze the conversion of sulfur-containing hydrocarbon feedstocks to lower molecular weight products and a regeneration reaction zone wherein the coke-deposited catalytic cracking catalyst particles are calcined at a temperature of 1000-. Wherein the rare earth component is prepared by treating bastnasite to remove at least 50% of fluorine therein. Although the sulfur transfer agent has a higher sulfur transfer activity. However, the biggest problem in the preparation process is that more than 50% of fluorine in the bastnasite must be removed first, the occurrence of toxic gas fluorine causes much trouble to the industrial preparation of the transfer agent, and the handling of fluorine causes resistance to the industrial production of the transfer agent.
USP4,606,813 discloses a fluid catalytic cracking catalyst comprising a mixture of a catalytically active first component and a second component capable of reducing sulfur oxide emissions in the regenerator, the catalyst comprising (1)10 to 70% by weight of a fluidizable particle comprising at least 40% by weight of faujasite and (2)30 to 90% by weight of a second fluidizable particle comprising at least 70% by weight of a "balance" specific surface area of 40 to 100 meters2Per gram of alumina. The specific surface area of the balance is 40-100 m2The alumina/g can be alumina obtained by calcining α -alumina trihydrate at a temperature of 750 DEG F and 1200 DEG F for at least 1 hour, the catalyst can also contain lanthanum, cerium, neodymium, praseodymium, samarium, dysprosium, platinum, ruthenium, rhodium, palladium, osmium, iridium or mixtures thereof, in order to increase the attrition resistance of the second component, one of the preparation methods comprises calcining a commercially available alumina component under steam at a temperature of 750 DEG F and 1200 DEG F for at least 1 hour, and the other preparation method comprises calcining a commercially available alumina component again at a temperature of 750 DEG F and 1200 DEG FHydrating, pulping with water, heating at 150 deg.F and pH of 9.3-9.5 for 6-6.5 hr, filtering, washing and drying. If the metal component is contained as described above, the metal component may be introduced by an impregnation method.
USP4, 589, 978 discloses sulfur transfer agents consisting essentially of rare earth metal oxides and their preparationThe sulfur transfer agent comprises cerium or a combination of cerium and lanthanum, the rare earth metal can be supported on an inert material, preferably a metal oxide such as alumina as SO3The adsorbent of (1). The alumina may be gamma, eta, and theta alumina. The carrier of the rare earth oxide and the alumina is selected from silica, silica-alumina, zeolite, diatomite or alumina. The preparation method comprises soaking the carrier with appropriate amount of metal salt, or mixing rare earth and alumina or its precursor, mixing the mixture with gel of the carrier, and spray drying.
As mentioned above, in the fluid catalytic cracking process, since the sulfur transfer agent circulates together with the catalytic cracking catalyst between the reactor and the regenerator, in order for the sulfur transfer agent to function better, the sulfur transfer agent must have high wear resistance in addition to high sulfur transfer activity. Only sulfur transfer agent with good abrasion resistance can reduce the loss of the sulfur transfer agent in the reaction process, reduce the supplement amount of the transfer agent and save the cost of the whole fluid catalytic cracking process.
The invention aims to provide a preparation method of a novel sulfur transfer catalyst with better abrasion resistance.
The preparation method of the sulfur transfer agent provided by the invention comprises the steps of soaking a hydrated alumina microsphere by using a solution containing a cerium compound, drying and roasting, wherein the preparation method of the hydrated alumina microsphere comprises the following steps:
(1) mixing part of pseudoboehmite in a preset amount with deionized water to prepare slurry with the solid content of 5-30 wt%, adding an acid, adjusting the pH value of the slurry to 1.5-4.0, adding the rest pseudoboehmite, and stirring until the slurry is in a uniform colloid state, wherein the weight ratio of the pseudoboehmite added successively is 0.1-5 in terms of alumina;
(2) adding aluminum sol under stirring, wherein the weight ratio of the pseudo-boehmite to the aluminum sol is 1-50 in terms of aluminum oxide;
(5) aging the slurry at 30-100 deg.C for more than 0.5 hr.
(6) Spray drying and forming to prepare the hydrated alumina microspheres.
Wherein the acid used for adjusting the pH value is selected from one or more of water-soluble inorganic acid and organic acid. The common acid is one or more of hydrochloric acid, nitric acid and acetic acid. Among them, hydrochloric acid or nitric acid is more preferable.
Wherein the weight ratio of the successively added pseudo-boehmite is 0.1-5, more preferably 0.3-3, calculated on the basis of alumina. The weight ratio of pseudo-boehmite to alumina sol is 1 to 50, more preferably 5 to 35, in terms of alumina.
The aging temperature after the addition of the aluminum sol is 30 to 100 ℃, more preferably 40 to 80 ℃, and the aging time is more than 0.5 hour, more preferably 0.5 to 4 hours.
The slurry may have a solids content of 5 to 30% by weight, preferably 10 to 20% by weight.
The spray drying and forming of the slurry is carried out by conventional methods and conditions, generally under the conditions of controlling the temperature of the tail gas to be 250-300 ℃ and the spray pressure to be 50-60 atmospheric pressure.
The solution containing cerium compound is used for impregnating the hydrated alumina microspheres, and the existing method for impregnating alumina can be adopted, and only the alumina is replaced by the hydrated alumina microspheres. The drying and firing after the impregnation are carried out under conditions conventional in the art. For example, the drying temperature may be from room temperature to 300 ℃, preferably 100-.
The cerium compound-containing solution is used in an amount such that the final sulfur transfer agent has a conventional cerium content, typically as CeO2Meter, of the cerium-containing solutionThe amount used is such that the cerium content in the final sulfur transfer agent is 5 to 30% by weight, preferably 10 to 25% by weight. The cerium compound is selected from one or more soluble cerium compounds, and preferably, the cerium compound is selected from one or more of cerium trichloride and ammonium cerium nitrate with or without crystal water.
The method provided by the invention has the outstanding advantage that the wear resistance of the sulfur transfer agent prepared by the method is greatly improved. For example, the sulfur transfer agent prepared by the method provided by the invention has a wear index of only 0.8-1.1%-1. While sulfur transfer agents prepared by prior art methods, including the method disclosed in USP 4606, 813, all have abrasion indices above 3 percent-1。
Another outstanding advantage of the process provided by the present invention is that the sulfur transfer agent prepared by the process has higher sulfur uptake activity and sulfur release activity. For example, sulfur uptake activity of sulfur transfer agents prepared by the process provided by the present invention is 73-76 mole% under oxidation conditions similar to those in catalytic cracking regenerators, whereas sulfur uptake activity of catalysts prepared using the prior art is only 38-67 mole%. Thesulfur-releasing activity of the sulfur transfer agent prepared by the process provided by the present invention is 19-24 mole% under reducing conditions similar to those in a catalytic cracking reactor, whereas the sulfur-releasing activity of the catalyst prepared by the prior art is only 10-14 mole%.
In the conventional method for producing a sulfur transfer agent, generally, hydrated alumina is first molded, dried and calcined to form an alumina support, the alumina support is then impregnated with a solution containing a metal component, and then, the alumina support is dried and calcined for the second time (the production process is shown in fig. 1). The reason for this is that hydrated alumina prepared by the prior art method is easily hydrated when impregnated with a solution containing a metal component, and on the one hand, hydrated alumina comes off from a molded article, and on the other hand, hydrated alumina on different particles are bonded to each other, so that the particles are adhered together, which seriously damages the shape of the carrier, thereby affecting the wear resistance thereof. Therefore, the method in the prior art has the disadvantages of two times of roasting, complex steps and more energy consumption. The present invention adopts a special method to obtain a hydrated alumina microsphere, then uses aqueous solution containing metal to impregnate said hydrated alumina microsphere, then dries and calcines (its preparation process is shown in figure 2). When the method provided by the invention is used for dipping the metal component, the hydrated alumina microsphere is not hydrated and still keeps the original shape. The sulfur transfer agent obtained by impregnating the cerium component and roasting not only has higher wear resistance and sulfur transfer activity than the prior art, but also reduces a roasting step and saves energy. Therefore, the method provided by the invention has the further outstanding advantages of simplicity, suitability for large-scale industrial production and energy conservation.
FIG. 1 is a schematic flow diagram of a prior art sulfur transfer agent preparation process;
FIG. 2 is a schematic flow diagram of a sulfur transfer agent preparation process provided by the present invention;
the following examples further illustrate the invention.
Example 1
This example illustrates the preparation of hydrated alumina microspheres.
Adding 18 kg of deionized water into a 50L pulping tank, and adding 13 kg of pseudo-boehmite (Al) under stirring2O332.8 wt%, manufactured by Zhou village catalyst factory), stirring uniformly to prepare slurry with solid content of 13.8 wt%, adding 21 wt% hydrochloric acid (chemical purity, manufactured by Beijing chemical plant), and adjusting pH = 1.8. 13 kg of the above pseudo-boehmite was added under stirring to make the slurry in a uniform colloidal state. 5 kg of aluminium sol (Al) are added with stirring2O3Content 21.8 wt%, manufactured by Zhou village catalyst factory) was stirred uniformly. The weight ratio of the added pseudo-boehmite to the added pseudo-boehmite is 1 and the weight ratio of the added pseudo-boehmite to the added alumina sol is 7.8 in terms of alumina. After aging the slurry at 60 ℃ for 2 hours, the spray pressure was adjusted to 260 ℃ as the tail gas temperatureSpray drying and forming under the condition of 50 atmospheric pressure to obtain the hydrated alumina micro-particlesBall X1。
Example 2
This example illustrates the preparation of hydrated alumina microspheres.
1.8 kg of deionized water was added to a 50L pulping jar, and 3 kg of pseudo-boehmite (Al) was added under stirring2O332.8 wt%, manufactured by Zhou village catalyst factory), stirring uniformly, adding 0.4 kg of deionized water to prepare slurry with the solid content of 18.9 wt%, adding 21 wt% hydrochloric acid (chemical purity, manufactured by Beijing chemical plant), and adjusting the pH of the slurry to = 3.5. Adding 3 kg of pseudo-boehmite under stirring, continuing stirring to make the slurry in a uniform colloidal state, and adding 0.3 kg of alumina sol (Al) under stirring2O3Content 21.8 wt%, manufactured by Zhou village catalyst factory), and stirring uniformly. The weight ratio of the added pseudo-boehmite to the added pseudo-boehmite is 1 and the weight ratio of the added pseudo-boehmite to the added alumina sol is 30 in terms of alumina. After aging the slurry at 45 ℃ for 0.5 hour, spray-drying and forming under the conditions that the tail gas temperature is 280 ℃ and the spray pressure is 60 atmospheres to obtain hydrated alumina microspheres X2。
Example 3
This example illustrates the preparation of a sulfur transfer agent.
23.84 g of CeCl3·7H2O was dissolved in 40 ml of deionized water, and 100 g (65.74 wt% in terms of solid content) of the hydrated alumina microspheres X prepared in example 1 were impregnated with the resulting solution1. Then, drying for 2 hours at the temperature of 120 ℃, and roasting for 3 hours at the temperature of 600 ℃ to obtain the sulfur transfer agent A prepared by the method provided by the invention. CeO in sulfur transfer agent A2The contents, specific surface of the sulfur transfer agent A, abrasion index, average particle diameter (average particle diameter for short), and bulk ratio are shown in Table 1. Wherein the specific surface is measured by a low-temperature nitrogen adsorption BET method. The wear index was determined by RIPP29-90 (see "analytical methods in petrochemical industry (RIPP test methods)", scientific Press,73-75, 1990). The average particle diameter was measured by means of a laser particle sizer model 3600E (product of Markov, England).
Example 4
This example illustrates the preparation of a sulfur transfer agent.
Adding 53.2 g of (NH)4)2Ce(NO3)6(chemical purity, Beijing chemical plant) was dissolved in 40 ml of the solution140 g of the hydrated alumina microspheres X prepared in example 1 were impregnated with the resulting solution in deionized water1(solid content 65.74 wt%). Then, the sulfur transfer agent B is dried for 2 hours at the temperature of 120 ℃ and roasted for 3 hours at the temperature of 600 ℃ to obtain the sulfur transfer agent B prepared by the method provided by the invention. CeO in sulfur transfer agent B2The contents, specific surface of sulfur transfer agent B, abrasion index, average particle diameter and bulk ratio are shown in Table 1.
Example 5
This example illustrates the preparation of a sulfur transfer agent.
A sulfur transfer agent was prepared as in example 4, except that (NH)4)2Ce(NO3)6The amount of (b) was 68.85 g, giving a sulfur transfer agent C prepared by the method provided by the present invention. CeO in sulfur transfer agent C2The contents, specific surface of sulfur transfer agent C, abrasion index, average particle diameter and bulk ratio are shown in Table 1.
Example 6
This example illustrates the preparation of a sulfur transfer agent.
A sulfur transfer agent was prepared as in example 3, except that the hydrated alumina microspheres X prepared in example 1 were replaced with the hydrated alumina microspheres X2 (again, having a solids content of 65.74% by weight) prepared in example 21To obtain the sulfur transfer agent D prepared by the method provided by the invention. CeO in sulfur transfer agent D2The contents, specific surface, abrasion index, average particle diameter and bulk ratio of the sulfur transfer agent D are shown in Table 1.
Comparative example 1
This comparative example illustrates the preparation of a reference sulfur transfer agent.
Adding 18 kg of deionized water into a 50L pulping tank, and adding 13 kg of pseudo-boehmite (Al) under stirring2O332.8 wt%, produced by Zhou village catalyst factory), and is stirred uniformly to prepare slurry with the solid content of 13.8 wt%. Hydrochloric acid (chemical purity, manufactured by beijing chemical plant) was added at a concentration of 21 wt%, the pH of the slurry was adjusted to =1.8, and stirring was continued to make the slurry uniform in a colloidal state. And (3) after aging the slurry at 60 ℃ for 1 hour, spray-drying and forming under the conditions that the tail gas temperature is 260 ℃ and the spray pressure is 50 atmospheric pressures to obtain the reference hydrated alumina microspheres. 23.84 g of CeCl3·7H2O was dissolved in 40 ml of distilled water, and 109.6 g of the obtained reference hydrated alumina microspheres (solid content 60 wt%) were impregnated with the obtained solution. Then drying at 120 deg.C for 2 hr, and calcining at 600 deg.C for 3 hr to obtainTo reference sulfur transfer agent E. CeO in reference sulfur transfer agent E2The contents, specific surface, abrasion index, average particle diameter and bulk ratio of the sulfur transfer agent E are shown in Table 1.
Comparative example 2
This comparative example illustrates the preparation of a reference sulfur transfer agent.
The reference sulfur transfer agent was prepared according to the method of comparative example 1 except that the obtained reference hydrated alumina microspheres were calcined at 600 ℃ for 3 hours before impregnation to convert them into alumina, followed by impregnation to obtain the reference sulfur transfer agent F. CeO in sulfur transfer agent F2The contents, specific surface of the sulfur transfer agent F, the bulk ratio, the abrasion index, the average particle diameter and the bulk ratio are shown in Table 1.
Comparative example 3
This comparative example illustrates the preparation of a reference sulfur transfer agent.
Hydrated alumina microspheres, which are manufactured by Condea, Germany and have a trade name of SB, are calcined at 600 ℃ for 3 hours to obtain an alumina carrier. 23.84 g of CeCl3·7H2Dissolving O in 40 ml of distilled water to obtain65.74G of the obtained alumina carrier was impregnated with the solution, dried at a temperature of 120 ℃ for 2 hours, and calcined at a temperature of 600 ℃ for 3 hours to obtain a reference sulfur transfer agent G. CeO in sulfur transfer agent G2The contents, specific surface of the sulfur transfer agent G, abrasion index, average particle diameter and bulk ratio are shown in Table 1.
Comparative example 4
This comparative example illustrates the preparation of a reference sulfur transfer agent.
23.84 g of CeCl3·7H2Dissolving O in 40 ml of distilled water, impregnating 96 g of α -gibbsite microspheres (solid content is 68.48 weight percent) produced by Shandong aluminum works with the obtained solution, drying at 120 ℃ for 2 hours, and roasting at 600 ℃ for 3 hours to obtain a reference sulfur transfer agent H, wherein CeO in the sulfur transfer agent H2The contents, specific surface of the sulfur transfer agent H, abrasion index, average particle diameter and bulk ratio are shown in Table 1.
Comparative example 5
This comparative example illustrates the preparation of a reference sulfur transfer agent.
The microsphere α -gibbsite produced by Shandong aluminum plant is roasted for 3 hours at 600 ℃ to obtain an alumina carrier, 23.84 g of CeCl is added3·7H2O was dissolved in 40 ml of distilled water, and 65.74 g of the obtained alumina carrier was impregnated with the obtained solution, dried at 120 ℃ for 2 hours, and calcined at 600 ℃ for 3 hours to obtain a reference sulfur transfer agent I. CeO in sulfur transfer agent I2The contents, specific surface of the sulfur transfer agent I, abrasion index, average particle diameter and bulk ratio are shown in Table 1.
Comparative example 6
This comparative example illustrates the preparation of a reference sulfur transfer agent.
The microspheres α -gibbsite, produced by Shandong aluminum works, were treated with 100% steam at 565 ℃ for 1 hour, 23.84 g of CeCl3·7H2O was dissolved in 40 ml of distilled water, and 96 g of the steam-treated product (solid content) was impregnated with the obtained solutionIn an amount of 68.48 wt%), dried at 120 ℃ for 2 hours and calcined at 600 ℃ for 3 hours to give the reference sulfur transfer agent J. CeO in sulfur transfer agent J2The contents, specific surface of the sulfur transfer agent J, abrasion index, average particle diameter andbulk ratio are shown in Table 1.
TABLE 1
| Examples of the invention Numbering | Transfer agent Numbering | CeO2Comprises Weight percent of | The specific surface area of the material is as follows, rice and its production process2Per gram | Wear finger A few,% of-1 | Bulk ratio | Average particle Diameter, Angstrom |
| 3 | A | 14.4 | 176 | 1.0 | 1.0 | 72.6 |
| 4 | B | 15.4 | 192 | 1.1 | 1.1 | 61.4 |
| 5 | C | 19.0 | 161 | 0.8 | 1.0 | 75.5 |
| 6 | D | 14.4 | 168 | 0.9 | 1.0 | 66.4 |
| Comparative example 1 | E | 14.4 | 142 | 5.4 | 0.6 | 65.4 |
| Comparative example 2 | F | 14.4 | 236 | 3.0 | 0.9 | 71.5 |
| Comparative example 3 | G | 14.4 | 220 | 6.1 | 0.6 | 57.0 |
| Comparative example 4 | H | 14.4 | 342 | 8.2 | 0.9 | 77.2 |
| Comparative example 5 | I | 14.4 | 333 | 7.5 | 0.9 | 78.3 |
| Comparative example 6 | J | 14.4 | 106 | 6.5 | 0.9 | 79.4 |
Examples 7 to 10
The following examples illustrate the sulfur transfer activity of the sulfur transfer agents prepared by the process provided by the present invention.
1. And (4) measuring the sulfur absorption activity of the sulfur transfer agent.
A part of each of the sulfur transfer agents (fresh sulfur transfer agents) A to D prepared in examples 3 to 6 was aged with 100% steam at a temperature of 760 ℃ for 6 hours to give aged sulfur transfer agents A to D. Fresh and aged sulfur transfer agents A-D were mixed with a cracking balance agent of the industrial brand MZ-3, respectively, the sulfur transfer agent accounting for 10% by weight of the mixture. Simulating the composition of catalytic cracking regenerated flue gas, preparing the regenerated flue gas containing SO22000ppm、O25% by volume, N294.8% by volume of the mixed gas. 30 g of a mixture of a sulfur transfer agent and MZ-3 or 30 g of MZ-3 is put into a small fixed fluidized bed reactor, the mixed gas is introduced into the reactor at the flow rate of 870 ml/min, the temperature of the reactor is controlled at 600 ℃, and the gas generated in the reaction is introduced into an absorption liquid (the absorption liquid contains H)2O21.2% by weight of H2O2Aqueous solution), SO2Is absorbed by the absorption liquid. The reaction was continued for 45 minutes. After the reaction was completed, the absorbent solution was titrated with 0.05N standard NaOH solution until the solution changed color (indicator is a composite indicator of methyl red and methylene blue). The sulfur-absorbing activity of the sulfur transfer agent was calculated according to the following formula.
SAa％=(SM-Sa)/SMWherein, SAaRepresenting the sulfur-absorbing activity of a certain sulfur transfer agent a. SaRepresenting the equivalent amount of NaOH consumed in a reactor charged with 30 grams of a mixture of a certain sulfur transfer agent a and MZ-3 catalyst. SMRepresenting the equivalent amount of NaOH consumed when 30 grams of MZ-3 catalyst was charged to the reactor.
2. Determination of sulfur releasing Activity of a sulfur transfer agent.
Will be at the topThe reactor after the completion of sulfur uptake in the above 1 was charged with N2After the temperature was lowered and controlled to be constant at 500 c, high-purity hydrogen was introduced, and the off-gas was introduced into 150 ml of an absorbing solution (which is an aqueous solution of zinc nitrate having a concentration of 0.01N) and the reaction was continued for 3 hours. The absorbed solution was filtered, and the zinc ions in the precipitate were washed with 100 ml of distilled water. Then, NH was added to the obtained filtrate in a volume ratio of 1: 1 to the filtrate at pH 103-NH4Cl buffer solution, and the filtrate to which the buffer solution was added (indicator is chrome black T) was titrated with 0.02N EDTA solution. The sulfur-releasing activity of the sulfur transfer agent was calculated by the following formula.
SDa％=(NM-Na)/NMWherein, SDaRepresenting the sulfur-releasing activity of a certain sulfur transfer agent a. N is a radical ofaRepresenting the equivalent amount of EDTA consumed in the reactor when a mixture of a certain sulfur transfer agent a and MZ-3 catalyst was charged after completion of sulfur uptake. N is a radical ofMSubstitute for Chinese traditional medicineThe equivalent amount of EDTA consumed in the sulfur-sorbed MZ-3 catalyst charged to the reactor.
Table 2 lists the sulfur-uptake activity and sulfur-release activity of the sulfur transfer agents A-D.
Comparative examples 7 to 12
The following comparative examples illustrate the sulfur uptake activity and sulfur release activity of the reference sulfur transfer agent.
The reference sulfur transfer agents E to J prepared in comparative examples 1 to 6 were aged in the same manner as in examples 7 to 10, and the sulfur-absorbing and sulfur-releasing activities of the reference sulfur transfer agents, both fresh and aged, were measured in the same manner as in examples 7 to 10, and the results are shown in Table 2.
TABLE 2
| Examples of the invention Numbering | Sulfur transfer agent Numbering | Fresh agent | Ageing agent | ||
| Sulfur absorption activity% | Sulfur release Activity% | Sulfur absorption activity% | Sulfur release Activity% | ||
| Example 7 | A | 73 | 20 | 43 | 20 |
| Example 8 | B | 76 | 19 | 46 | 25 |
| Example 9 | C | 70 | 24 | 44 | 25 |
| Example 10 | D | 75 | 20 | 52 | 24 |
| Comparative example 7 | E | 38 | 10 | 30 | 17 |
| Comparative example 8 | F | 60 | 10 | 43 | 17 |
| Comparative example 9 | G | 67 | 12 | 42 | 18 |
| Comparative example 10 | H | 59 | 14 | 47 | 14 |
| Comparative example 11 | I | 57 | 14 | 45 | 16 |
| Comparative example 12 | J | 51 | 11 | 44 | 15 |
Claims (8)
1. A method for preparing a sulfur transfer catalyst, comprising impregnating a hydrated alumina microsphere with a solution containing a cerium compound, drying and calcining, said aluminum hydroxide microsphere being prepared by a method comprising the steps of:
(1) mixing part of pseudoboehmite in a preset amount with deionized water to prepare slurry with the solid content of 5-30 wt%, adding an acid, adjusting the pH value of the slurry to 1.5-4.0, adding the rest pseudoboehmite, and stirring until the slurry is in a uniform colloid state, wherein the weight ratio of the pseudoboehmite added successively is 0.1-5 in terms of alumina;
(2) adding aluminum sol under stirring, wherein the weight ratio of the pseudo-boehmite to the aluminum sol is 1-50 in terms of aluminum oxide;
(3) aging the slurry at 30-100 deg.C for more than 0.5 hr.
(4) Spray drying and forming to prepare the hydrated alumina microspheres.
2. The method of claim 1, wherein the acid used to adjust the pH is selected from hydrochloric acid or nitric acid.
3. The method according to claim 1, wherein the weight ratio of the pseudoboehmite added in sequence to the alumina sol is 0.3-3 and the weight ratio of the pseudoboehmite to the alumina sol is 5-35, calculated as alumina.
4. The method according to claim 1, wherein the aging temperature after the addition of the aluminum sol is 40 to 80 ℃ and the aging time is 0.5 to 4 hours.
5. The method of claim 1, wherein the slurry has a solids content of 10-20 wt%.
6. The method of claim 1 wherein the CeO is used2The amount of the cerium-containing compound solution is such that the cerium content in the final sulfur transfer agent is 5-30 wt%.
7. The method of claim 6 wherein the CeO is used2The amount of the solution of the cerium-containing compound is such that the cerium content in the final sulfur transfer agent is 10-25% by weight.
8. The method as claimed in claim 1, 6 or 7, wherein the cerium compound is selected from one or more of cerium trichloride with or without crystal water, and ammonium cerium nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99123823A CN1102433C (en) | 1999-11-12 | 1999-11-12 | Process for preparation of sulfur transfer catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99123823A CN1102433C (en) | 1999-11-12 | 1999-11-12 | Process for preparation of sulfur transfer catalyst |
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| Publication Number | Publication Date |
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| CN1295877A true CN1295877A (en) | 2001-05-23 |
| CN1102433C CN1102433C (en) | 2003-03-05 |
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| CN99123823A Expired - Fee Related CN1102433C (en) | 1999-11-12 | 1999-11-12 | Process for preparation of sulfur transfer catalyst |
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| CN (1) | CN1102433C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7347930B2 (en) | 2003-10-16 | 2008-03-25 | China Petroleum & Chemical Corporation | Process for cracking hydrocarbon oils |
| US7435332B2 (en) | 2003-09-28 | 2008-10-14 | China Petroleum & Chemical Corporation | Process for cracking hydrocarbon oils |
| CN103920455A (en) * | 2013-01-14 | 2014-07-16 | 北京三聚环保新材料股份有限公司 | Method for preparing microsphere sulfur transfer agent with high activity and high wear resistance |
| CN114345292A (en) * | 2022-01-14 | 2022-04-15 | 润和科华催化剂(上海)有限公司 | Sulfur transfer agent with strong base site and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4497902A (en) * | 1979-04-11 | 1985-02-05 | Standard Oil Company (Indiana) | Composition for removing sulfur oxides from a gas |
| US4423019A (en) * | 1979-04-11 | 1983-12-27 | Standard Oil Company (Indiana) | Process for removing sulfur oxides from a gas |
| US4589978A (en) * | 1985-03-01 | 1986-05-20 | Mobil Oil Corporation | Catalyst for reduction of SOx emissions from FCC units |
-
1999
- 1999-11-12 CN CN99123823A patent/CN1102433C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7435332B2 (en) | 2003-09-28 | 2008-10-14 | China Petroleum & Chemical Corporation | Process for cracking hydrocarbon oils |
| US7347930B2 (en) | 2003-10-16 | 2008-03-25 | China Petroleum & Chemical Corporation | Process for cracking hydrocarbon oils |
| US9163182B2 (en) | 2003-10-16 | 2015-10-20 | China Petroleum & Chemical Corporation | Process for cracking hydrocarbon oils |
| CN103920455A (en) * | 2013-01-14 | 2014-07-16 | 北京三聚环保新材料股份有限公司 | Method for preparing microsphere sulfur transfer agent with high activity and high wear resistance |
| CN103920455B (en) * | 2013-01-14 | 2016-03-30 | 北京三聚环保新材料股份有限公司 | The preparation method of a kind of high activity and high-wearing feature microphere sulfur transfer agent |
| CN114345292A (en) * | 2022-01-14 | 2022-04-15 | 润和科华催化剂(上海)有限公司 | Sulfur transfer agent with strong base site and preparation method thereof |
| CN114345292B (en) * | 2022-01-14 | 2023-10-27 | 润和科华催化剂(上海)有限公司 | Sulfur transfer agent with strong base site and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1102433C (en) | 2003-03-05 |
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