KR20120062066A - Manufacture of zio-lite using wasted rfcc(resid fluidized catalytic cracking) catalyst - Google Patents

Abstract

PURPOSE: A method for manufacturing zeolite based on waste resid fluidized catalytic cracking(RFCC) catalyst is provided to prevent the occurrence of environmental pollution by recycling the waste RFCC catalyst which is an environmental pollutant. CONSTITUTION: Waste RFCC is directly ion-exchanged or is ion-exchanged after oxidization. The waste RFCC is composed of 60-70% of silicon dioxide, 25-32% of aluminum oxide, 0.1-0.5% of iron, 0.1-0.4% of nickel, and 0.1-0.4% of vanadium. The waste RFCC is generated from the oil petroleum refining process of a petrochemical industry. A hydrothermal synthesizing process, a washing process, a drying process, and a grinding process are implemented after the ion-exchanging process. A vibration mill and a centrifugal-vibration mill are used for the grinding process. Sodium hydroxide is used as a solvent during the hydrothermal synthesizing process.

Description

Manufacture of zio-lite using wasted Resid Fluidized Catalytic Cracking (RFCC) catalyst

The present invention relates to the preparation of zeolite using a waste fluidized bed catalytic cracking catalyst generated as a by-product in the oil refining process, in particular a waste fluidized bed generated and discarded in the process of hardening heavy oil during petroleum refining of petrochemical industry The present invention relates to a method for producing a conventional expensive zeolite using a catalytic decomposition catalyst.

The waste-flow catalytic catalytic cracking (RFCC) catalyst, which occurs during the refinery's heavy oil cracking process, is not used as a catalyst for metal oils in the carrier, unlike conventional petrochemical catalysts, but for heavy oil cracking using zeolite as a main component. In other words, vanadium, nickel, etc. in the heavy oil cracking process are accumulated and diffused on the surface of the fluid catalytic cracking catalyst, and thus the waste is discarded due to deterioration of the catalyst function. As a result, various studies are ongoing in terms of use development.

Originally, the waste RFCC catalyst produced in Korea has a very low content of about 3,000 ppm to 8,000 ppm of heavy metals, so leaching of heavy metals is not a problem. 44% of waste catalysts are landfilled, and 36% of the rest of cement raw materials are different. Sold as a catalyst to the RFCC plant, the remainder being used as asphalt fillers.

Since the waste RFCC catalyst mainly consists of silica and alumina, research is being conducted to recover the silica and use it as a catalyst, or to recover the alumina to manufacture zeolite. In Korea, the waste RFCC catalyst is recycled as a raw material of cement, but the added value is very low. Therefore, research on recycling method with high added value is underway, and there are regeneration technology of waste RFCC catalyst and valuable metal recovery research. In particular, the technology of regenerating permanent magnets has been commercialized outside the country.

On the other hand, zeolite synthesis can be largely divided into two types, one is the clay method using silicate clay mineral, and the other is a pure chemical method of hydrothermal synthesis using silicate and aluminate as raw materials. to be. In the clay method, the silicate clay mineral is amorphous by calcining or ultra fine grinding, and then synthesized in an alkaline solution. However, this method is difficult to remove iron oxides and impurities present in clay minerals, and there are also many difficulties in the conversion to the actual process. Pure chemical method has no reserve of bauxite, which is a raw material of alumina, in Korea, and it is inferior in competitiveness in view of economic feasibility. It is well known that synthetic zeolites are spotlighted as catalysts and as gaseous or liquid adsorbents, but natural zeolites, alumino-silicate minerals, have been used in many ways due to their mineral properties and chemical surface activity. It is a recent thing that has become highly appreciated.

Mineralogically, zeolites are alumina-silicates containing cations such as Na + and Ca ^{2 +} , and have a three-dimensional solid structure with a pore size of about 3 to 11, and contain moisture that can be removed. And, among the minerals, the cation exchange capacity (CEC) is 100-300 has the highest cation exchange capacity is known as a mineral having a high selective adsorption capacity for the gas. In addition, natural zeolites are useful as soil improvers, livestock feed, or feedstocks, and are highly regarded for their low hardness.

In addition, their use as adsorbents, humectants, ion exchangers, weight agents and molecular sieves is remarkable. In particular, the use of cation exchange capacity as a wastewater treatment agent, a radioactive wastewater treatment agent and a hard water softener is increasing day by day. In particular, the development of molecular sieves using natural zeolites has been widely studied in various ways.

Natural zeolites have many advantages as described above, but iron or other metal components are included as impurities, and crystal defects and pores are often blocked, and thus, sufficient surface area and cation exchange ability are often not shown. In addition, the type of zeolites produced is not diverse, which limits the development of high value products. Therefore, many attempts have been made to synthesize zeolites from cheap materials that are widely distributed in nature, such as kaolin, coal ash, volcanic ash, and are often discarded as waste.

The present inventors have found that the waste RFCC particles generated in the crude oil refining process of the petrochemical process have already decreased in particle size through the decomposition process. Was intended.

In particular, since the chemical composition and physical properties have properties suitable for the production of zeolite, it is intended to use the waste catalyst as it is, or by grinding and processing.

Physicochemical Properties of Waste RFCC Catalysts Pore particle size distribution 300-200
200-100
100-80
80-65
65-50
50-40
40-30
30-20 63.8%
17.3%
4.3%
0%
2.8%
1.4%
2.5%
3.5% Powder particle size distribution <10 μm
10 ~ 20㎛
20 ~ 40㎛
40 ~ 60㎛
60 ~ 80㎛
80 ~ 95㎛
95 ~ 110㎛
110 ~ 130㎛ 0.3%
1.4%
12.6%
31.6%
66.3%
83%
95%
100% Chemical composition Silicon dioxide
(SiO ₂ ) Aluminum oxide
(Al ₂ O ₃ ) iron
(Fe) nickel
(Ni) vanadium
(V) 60-70 25-32 0.1-0.5 0.1-0.4 0.1-0.4

As described above, the present invention is difficult to use because the conventional zeolite is very expensive, and therefore, while searching for a material for replacing the same, the waste fluidized bed catalytic decomposition catalyst generated during the petroleum refining process of the petrochemical industry is SiO ₂ and Al ₂ O _3. In addition, it is considered that Si / Al = 2.2 and porosity are relatively large. Therefore, when using waste catalyst, it is thought that it can give a role as resource recycling and high value-added functional material. It can be obtained by direct hydrolysis, washing or drying after being crushed or directly.

Accordingly, in view of the expensive inorganic zeolite raw materials, the cost of the existing raw materials can be reduced, and waste can be directly used as a main material for new functional materials. Therefore, an object of the present invention is to improve the economics, productivity and workability by using the waste catalyst discarded after use in the process of heavy oil decomposition of the oil refining company to improve zeolite production, increase the added value by recycling the waste catalyst, environmental The present invention provides a composition and a method for preparing zeolite using a waste catalyst that eliminates pollution and ensures stable supply of inexpensive raw materials.

As such, the present invention can manufacture an inexpensive zeolite material by replacing a conventionally expensive zeolite with a waste fluidized catalytic catalytic cracking catalyst which has been disposed in the land without any use, and is also an environmental pollutant for waste fluidized bed catalyst decomposition. By recycling the catalyst to make it more valuable, it contributes to the national economy and has a very beneficial effect on pollution prevention.

1 is a manufacturing process of zeolite using waste fluidized-bed catalytic decomposition catalyst
<Table 1> shows the physicochemical properties of waste fluidized bed catalyst
Table 2 shows the leaching of V by NaOH from spent RFCC catalyst.
<Table 3> shows leaching amount of Fe by NaOH from spent RFCC catalyst.
Table 4 shows the leaching amount of Ni by NaOH from spent RFCC catalyst.

Referring to the configuration of the present invention in detail as follows.

The present invention relates to a method for preparing zeolite using waste fluidized bed catalytic cracking (RFCC) catalyst which is generated and discarded during the petroleum refining process of the petrochemical industry. And drying.

When described in detail by the embodiment according to the present invention as follows, but is not limited to the embodiment.

Example 1

The RFCC waste catalyst used in this example was used in experiments using the RFCC waste catalyst (non-oxidation) and the RFCC (oxidation) oxidizing the RFCC waste catalyst, mainly RFCC (oxidation) and RFCC (non-oxidation) The experiment was conducted. In the case of oxidation, RFCC waste catalyst was placed in a furnace, and then used after maintaining the oxidation at 800 ° C for 4 hours. The leaching method is a method of leaching heavy metals in a catalyst using an acid to discharge them out of the pores of the catalyst and separating them, using a strong acid such as sulfuric acid, but the purpose of this embodiment is to preserve the activity of the catalyst, Sodium hydroxide (NaOH) was used for the purpose of removing impure metals.

First, RFCC (oxidation) and non-oxidation samples which were oxidized at 800 ° C were prepared. This was mixed with 20 g of sample and 200 ml of solution at a ratio of 1:10 by an analyzer ICP, and experimented at concentrations of 0.1N, 0.3N, 0,5N and 50 ° C, 70 ° C, and 90 ° C by adding NaOH, respectively. The leaching was carried out for 10 minutes, 30 minutes, and 60 minutes, and V, Fe and Ni were examined. After leaching, the mixture was washed three times with distilled water and dried in an oven at 80 ° C.

The leached components were examined for size and shape by X-ray diffraction and electron microscopy, and the amount of cation exchange of the product was also determined by CEC measurement.

Elution of V gradually increased with increasing time and concentration, and the amount of V was higher in non-oxidation than in oxidation.

Amount of V leaching by NaOH from spent RFCC catalyst (unit: ppm) V 10 minutes 30 minutes 60 minutes 50 ℃ 0.1N 44.067 40.19 41.959 50 ℃ 0.1N (oxidation) 39.351 38.7 38.619 50 ℃ 0.3N 36.769 39.325 68.854 50 ℃ 0.3N (oxidation) 36.363 40.502 46.192 50 ℃ 0.5N 46.645 53.356 58.973 50 ℃ 0.5N (oxidation) 42.515 51.179 54.367 V 10 minutes 30 minutes 60 minutes 70 ℃ 0.1N 41.707 40.915 41.331 70 ℃ 0.1N (oxidation) 39.335 40.393 41.6 70 ℃ 0.3N 43.136 48.981 55.292 70 ℃ 0.3N (oxidation) 44.235 49.38 56.944 70 ℃ 0.5N 19.39 55.498 64.377 70 ℃ 0.5N (oxidation) 44.189 49.394 59.777 V 10 minutes 30 minutes 60 minutes 90 ℃ 0.1N 42.803 43.632 43.9 90 ℃ 0.1N (oxidation) 37.668 93.211 37.383 90 ℃ 0.3N 48.795 52.35 57.897 90 ℃ 0.3N (oxidation) 49.867 41.846 55.211 90 ℃ 0.5N 58.936 63.502 65.741 90 ℃ 0.5N (oxidation) 55.683 0.718 63.98

In the case of the amount of Fe eluted at a constant temperature (70 ° C.), it can be seen that the amount tends to decrease as the concentration increases. It can also be seen that the increase in time has little effect. In addition, a large amount of elution occurred at a low concentration of 0.1 N, and the amount of leaching of (b) oxidation as compared with the non-oxidation of the presence or absence of oxidation (a) showed that a large amount of Fe appeared when the concentration was low.

In general, the amount of Fe eluted at a constant temperature is low regardless of oxidation and non-oxidation at low temperature of 50 ℃, and the concentration of Fe is increased in the order of 0.1N, 0.3N, and 0.5N. And it was found.

Leaching amount of Fe by NaOH from waste RFCC catalyst (unit: ppm) Fe 10 minutes 30 minutes 60 minutes 50 ℃ 0.1N 0.772 0.501 0.551 50 ℃ 0.1N (oxidation) 0.593 0.517 0.57 50 ℃ 0.3N 0.295 0.324 0.585 50 ℃ 0.3N (oxidation) 0.418 0.443 0.435 50 ℃ 0.5N 0.157 0.232 0.305 50 ℃ 0.5N (oxidation) 0.268 0.225 0.171 Fe 10 minutes 30 minutes 60 minutes 70 ℃ 0.1N 0.463 0.447 0.45 70 ℃ 0.1N (oxidation) 0.586 0.592 0.646 70 ℃ 0.3N 0.381 0.391 0.392 70 ℃ 0.3N (oxidation) 0.422 0.439 0.412 70 ℃ 0.5N 0.293 0.402 0.266 70 ℃ 0.5N (oxidation) 0.21 0.228 0.266 Fe 10 minutes 30 minutes 60 minutes 90 ℃ 0.1N 0.409 0.452 0.605 90 ℃ 0.1N (oxidation) 0.333 0.377 0.424 90 ℃ 0.3N 0.299 0.323 0.404 90 ℃ 0.3N (oxidation) 0.272 0.314 0.342 90 ℃ 0.5N 0.395 0.323 0.397 90 ℃ 0.5N (oxidation) 0.199 0 0.252

When the concentration and time were increased at a constant temperature (50 ° C.), the amount of Ni eluted showed a large amount of elution at high concentrations, and the amount gradually increased with time. In addition, it was found that when the non-oxidation and the oxidation were compared, elution increased in the oxidized sample.

Overall, when the low concentration of 0.1N sample was first started (10 minutes), the elution amount was 0.3N and 0.5N sequentially, and also increased slowly as time increased (10 ~ 60). . Ni elution of each sample of 0.1N, 0.3N, and 0.5N at constant temperature increased slowly with time, and the amount of oxidation related to the presence or absence of oxidation was about 0.3 ~ 1ppm.

It is understood that the elution amount of Ni increases with increasing concentration, and the elution amount increases with time. In addition, when the temperature increases, the amount of elution tends to increase. In the case of oxidation and non-oxidation according to the presence or absence of oxidation, more Ni elution occurs in oxidation than non-oxidation.

Leaching amount of Ni by NaOH from spent RFCC catalyst (unit: ppm) Ni 10 minutes 30 minutes 60 minutes 50 ℃ 0.1N 0.359 0.674 0.721 50 ℃ 0.1N (oxidation) 0.802 0.951 0.985 50 ℃ 0.3N 1.2 1.66 3.286 50 ℃ 0.3N (oxidation) 2.133 2.44 2.557 50 ℃ 0.5N 2.149 2.373 2.317 50 ℃ 0.5N (oxidation) 2.706 2.91 2.827 Ni 10 minutes 30 minutes 60 minutes 70 ℃ 0.1N 0.649 0.726 0.73 70 ℃ 0.1N (oxidation) 1.022 1.012 1.061 70 ℃ 0.3N 1.742 1.985 2.229 70 ℃ 0.3N (oxidation) 2.573 2.688 2.805 70 ℃ 0.5N 2.248 2.358 2.535 70 ℃ 0.5N (oxidation) 2.801 2.709 2.994 Ni 10 minutes 30 minutes 60 minutes 90 ℃ 0.1N 0.71 0.714 0.757 90 ℃ 0.1N (oxidation) 0.825 0.848 0.88 90 ℃ 0.3N 1.986 2.102 2.259 90 ℃ 0.3N (oxidation) 2.636 2.784 2.702 90 ℃ 0.5N 2.377 2.444 2.327 90 ℃ 0.5N (oxidation) 3.013 0 2.738

Example 2

In this example, hydrothermal synthesis was used as a raw material of the RFCC waste catalyst. The method is as follows. 1 g of oxidized RFCC spent catalyst is placed together with caustic soda in a 2.5 cm diameter Teflon liner in a stainless steel container with a height of 6.5 cm2 and an inner radius of 2.6 cm. At this time, the caustic soda is made into an aqueous solution of the desired concentration and the container is completely sealed and subjected to hydrothermal reaction while changing the reaction temperature and time in a forced circulation oven. After the synthesis, the mixture is washed 5 times or more with distilled water and dried in an oven at 80 ° C for 24 hours.

The XRD patterns of the oxidized and non-oxidized RFCC spent catalysts showed characteristic peaks of typical phagesites, and the 2θ values were convexly raised between 20 and 30, indicating that the glassy silica-alumina component was present. have. The XRD patterns of the oxidized and non-oxidized samples showed almost similar shapes, and the non-oxidation showed an amorphous pattern due to the large content of heavy metals.

First, the oxidized RFCC waste catalyst was hydrothermally synthesized with caustic soda as a raw material, and the powder components were examined by XRD and SEM.

XRD of the product reacted by changing the concentration of NaOH aqueous solution for 48 hours at 90 ℃, it was confirmed that even in the 1M NaOH, even the original crystalline components disappeared, and in 2M and 3M NaOH relatively high purity We can see that Jersey site is created. On the other hand, the same temperature and time were synthesized, but sodalite was formed together at 4M NaOH concentration, and when only 5M or more, only sodalite appeared.

The result of reacting for 48 hours at 100 ° C., although the temperature difference is not large, it can be seen that the results are very different. At 90 ° C and 2M, the phagesite is cleanly obtained, but at 10 ° C and 100 ° C, 2M, GIS is mixed with the phagesite. Likewise, at 90 ° C and 5M, sodalite is purely obtained. Kancleanite comes out at 5 degreeC by 5 degreeC. It can be seen that the sensitivity of the reaction temperature changes the type of zeolite produced even at a small temperature difference.

All four types of zeolites were obtained when the temperature and concentration were different from each other under the same conditions (48-hour synthesis, 5 NaOH concentrations).

At low temperature and low concentration of NaOH, only pausite could be obtained cleanly. Sodalite was synthesized at a relatively low temperature of 90 ° C. and concentration of 5M. Optimum conditions for the production of the fuzzer site are 90 ° C and 3M NaOH, and at 100 ° C, it is shown together with the fusersite.

As a result of XRD, it is shown that the powderysite is best synthesized at 3M and 90 ° C, and sodalite is well formed at 5M and 90 ° C. Therefore, after two zeolites were synthesized under the conditions in which each zeolite was best synthesized, the crystal shape was confirmed through an electron microscope.

GIS electron micrographs and sodalite photographs show that both have been converted to zeolites, and their size is distributed in a round shape. Scanning electron micrographs of kancleanite shows that its surface is in the form of a typical kancleanite rod.

The experiment was performed three times, GIS showed the highest ion exchange rate of 430 Mmeq / 100g, and the fuser site also showed high CEC value of 300 or more. In comparison, kancleanite and sodalite showed relatively low values.

&Lt; Example 3 >

Cation exchange capacity (CEC) was measured, and the measuring method is as follows. Place the filter paper in the stirrer and make the filter surface freely so that it is about 1 cm thick at the bottom of the column. Slightly add 1 N ammonium acetate leachate, add about 0.2 g of sample, connect the column to the leach bottle, open the coke and wash it in the same way with 100 ml. At this time, the leaching time should be completed within 2 ~ 24 hours, and after leaching, it is washed in the same way with 100ml of 80% ethanol.

After washing, transfer the sample to the Kjeldahl flask with filter paper, add 0.5 g of magnesium oxide powder, add 300 ml of distilled water together, and take 50 ml of 4% boric acid solution into the Erlenmeyer flask and distill. At this time, when the distillate is about 200 ml, the distillation is completed and the Erlenmeyer flask is removed. The point of equivalence is the addition of a mixed indicator and Bromocre-sol green to the Erlenmeyer flask, titration with 1N sulfuric acid standard solution and a change from green to purple.

The cation substitution capacity is a measure of the number of negatively charged aluminum ions by exchange with Na ⁺ or other cationic ammonium ions present in the sample. In this analysis experiment, ammonium acetate was used as the ion exchange solution. After ion exchange, the solution was titrated by washing with ethyl alcohol to remove ammonium ions or acetate ions on the surface.

Cation exchange capacity test result sample Cation exchange capacity (cmol / kg) Oxidation One 0.1N, 50 ℃ 22.5 2 0.1N, 70 ℃ 27.4 3 0.1N, 90 ℃ 33.8 4 0.3N, 50 ℃ 57.0 5 0.3N, 70 ℃ 46.8 6 0.3N, 90 ℃ 46.2 7 0.5N, 50 ℃ 82.4 8 0.5N, 70 ℃ 82.9 9 0.5N, 90 ℃ 95.6 Deoxidation 10 0.1N, 50 ℃ 13.7 11 0.1N, 70 ℃ 18.4 12 0.1N, 90 ℃ 16.6 13 0.3N, 50 ℃ 31.2 14 0.3N, 70 ℃ 39.6 15 0.3N, 90 ℃ 34.7 16 0.5N, 50 ℃ 51.5 17 0.5N, 70 ℃ 68.9 18 0.5N, 90 ℃ 82.3

1) Resid Fluidized Catalytic Cracking (RFCC): Catalytic decomposition catalyst for fluidized bed
2) SEM (Scanning Electron Microscopy): Projection Electron Microscope
3) X-ray diffraction (XRD): X-ray diffraction

Claims (3)

The chemical composition of petroleum refining process is 60 ~ 70% of silicon dioxide (SiO ₂ ), 25 ~ 32% of aluminum oxide (Al ₂ O ₃ ), 0.1 ~ 0.5% of iron (Fe), nickel (Ni) The first step is to grind the waste fluidized-phase catalytic decomposition catalyst composed of 0.1 to 0.4% and 0.1 to 0.4% of vanadium (Fe) directly or after oxidation, and the second step and the washing step are the third step and hydrothermal synthesis. And a drying process as a fourth step and a reducing step as a fifth step.
Method for using a vibration mill and centrifugal vibration mill having mechanical chemistry when grinding the waste fluidized bed catalyst decomposition catalyst of claim 1.
When the hydrothermal synthesis using a solvent as sodium hydroxide (NaOH).

Images