Method of regenerating coke-contaminated catalyst with simul-taneous combustion of carbon monoxide

The invention herein relates to a process for regenerating a cracking catalyst.

The field of the invention is the processing of hydrocarbons by catalytic cracking.

The regeneration methods, in which a coke-impregnated catalyst is regenerated in a regeneration zone, occupy a large range of chemical methods. Particularly common are the regeneration methods used to regenerate a fluidizable catalytic cracking catalyst, impurized with coke in a regeneration zone, in a fluidized catalytic cracking (FCC) process.

Until the last years, - in the matter, it was, first of all, to remove the maximum quantity of coke from the consumed catalyst and, at the same time, to avoid excessive levels of temperature, resulting from the conversion of carbon oxide to carbon dioxide in certain parts of the regeneration zone, especially in the diluted phase catalyst region, where little catalyst is found for absorbing the reaction heat and where, therefore, it may result in thermal damage to cyclones or other separation equipment. The conversion, at most of a full-part cracking catalyst, of carbon dioxide into ordinary regeneration areas has been prevented quite simply by limiting the amount of fresh 5-fold regeneration gas entering the regeneration zone. Without the existence of sufficient oxygen for the determination of the oxidation of carbon oxide to carbon dioxide, the postardation cannot, regardless of the temperature in the regeneration zone, have a chance. Likewise, the temperatures in the regeneration area were generally limited to less than 675 ° C, by choosing working conditions in the reaction zone of hi15 drocarbons or fresh batch currents or recycle currents or some combinations thereof to limit the amount of coke on the catalyst consumed, and thus a ²⁰ quantity of fuel burned in the regeneration area. The exhaust gas produced, containing several percent by volume of carbon oxide, was allowed to escape either directly into the atmosphere or used as fuel in a carbon oxide burner, located at the bottom of the regeneration zone. Common practice, they start the cracking process as³⁰ fluidized thallium (FCC), familiar to specialists in such processes, has 72500

PRICE LEI 4, G0 • C state in the initial manual adjustment of the fresh regeneration gas current for the regeneration zone in insufficient quantity to determine the conversion, especially complete, of the carbon oxide, while limiting the temperatures in the regeneration zone to no more than 675 ° C. After the steady state control of the fluidized catalytic cracking process was obtained, the fresh regeneration gas flow rate was regulated, then, precisely, by a direct control responsible for a small temperature difference between the gas outlet temperature. escape (or the temperature of the separation space in the diluted phase) and the dense bed temperature to automatically maintain this fresh regeneration gas flow rate, In order to avoid complete conversion of carbon oxide to carbon dioxide, anywhere in the regeneration area. If the temperature difference increased above a certain predetermined temperature difference, thereby indicating a higher conversion of the carbon oxide to the diluted phase, the amount of fresh regeneration gas was reduced to prevent the complete conversion of carbon oxide to the dioxide. carbon. As this method shows a small amount of oxygen in the exhaust gas, generally in the range of 0.1 to 1% by volume of oxygen, it prevents the complete conversion of carbon oxide to carbon dioxide in the regeneration zone. .

The use of zeolite-containing catalysts for fluidized catalytic cracking processes, which are more ternrostable and have lower tendencies for coke production and the use of higher temperatures in the hydrocarbon conversion area, has, however, often recommended the application of additional heat in the fluidized bed catalytic cracking process. In a typical way, the additional heat was produced by external combustion of fuel in the regeneration zone or by adding or, increasing the amount of preheated charge in the preheater., By external charge. Thus, the heat was added and then later removed from the process, through two external installations, a charge preheater and a carbon oxide burner. The catalyst regeneration processes, described in the literature, have recognized the benefits of the conversion, particularly complete, of carbon oxide to carbon dioxide and the recovery of at least part of the combustion heat of carbon oxide in the regeneration zone. .

The advantages of these processes are now well known. These regeneration processes allow the reduction or elimination of the preheating of the batch, the elimination of air pollution with carbon οχι carbon, without the need for external carbon oxide burners and, in the case of coupling with hydrocarbon reaction zones of modern design, they result in improved yields. of valuable products.

The regeneration processes that use carbon oxide conversion promoters or catalysts for this are not new. Indeed, the processes so far in the field, for the regeneration of fluidizable cracking catalysts, impurified with coke, have used such promoters or catalysts. For example , in a known fluidized catalytic cracking process, a physical mixture of minced particles from a cracking catalyst and particles separated from a carbon oxide oxidation catalyst onto the support material in a phase chip region is used. density of a regeneration area. In a process described in the literature, a mixture of a cracking catalyst and a crystalline alumina-silicate is used, containing an oxidation catalyst in its internal porous structure.

In another known process, two separate catalysts of different granulation and composition are used; a cracking catalyst and an oxidation catalyst for carbon oxide, preferably deposited on a support material. Also, the oxidation catalyst of carbon oxide deposited on the support is maintained in the regeneration zone and does not leave this area in the hydrocarbon reaction zone, as the crack catalyst does. Coke and carbon oxide are oxidized in the regeneration area, while minimizing carbon dioxide in the flue gas.

Thus, in the regeneration processes hitherto, carbon oxide oxidation promoters have been used in one of two ways; 1) on particles separated from a matrix or a support material, particles to be mixed with the fluidized cracking catalyst, and 2) as a part or component of the fluidized cracking catalyst as such.

7250U

The mixtures of cracking catalyst and carbon oxide oxidation promoters on the substrate tend to be uneven, which may lead to a concentration of carbon oxide in the smoke base exceeding the permitted limits. The use of a cracking catalyst containing as component a pre-determined concentration of a carbon oxide oxidation promoter makes it difficult to establish in an regeneration zone the optimal concentration of oxidation promoter, suitable for the operating characteristics of this zone.

The process according to the invention eliminates these disadvantages, in that it performs the treatment of the catalyst in a regeneration zone, at a temperature of 590. , 79CFC and at a pressure between atmospheric pressure and 4.5 at, with a regeneration gas containing oxygen, which is introduced with a flow rate corresponding to a quantity of 4.5 ... 7.7 kg air / kg coke per unit of time, together with an oxidation promoter, consisting of a platinum or palladium compound in an organic solvent, such as; 1-butanol or 2-ethyl-1-hexanol in a concentration corresponding to 0.1 ... 15 ppm elemental metal, based on the amount of catalyst,

6 examples of the invention are given below.

Example I. Use a vessel in the form of a vertical tube, the upper end of which is provided with a porous stainless steel filter, to maintain in the vessel during operation the sample of catalyst that has been loaded into the vessel, and the lower end of which has an inlet device for the fluidizing medium (nitrogen or air) and an inlet device for the liquid containing the promoter. Measures were taken for heating the vessel at a constant temperature and a chromatographic apparatus was provided for taking samples and analyzing the exhaust gas from the vessel with respect to carbon oxide, carbon dioxide and oxygen, being obtained thereby. , a moment composition for characterizing the reduction of carbon oxide concentration. Each test was performed with a sample of 500 g of cracked catalyst consumed, containing impure zeolite with 0.9% coke. The coke was deposited on the catalyst by passing a batch of diesel over the clean regenerated catalyst, within a reaction area of ​​a pilot plant, operating under standard, predetermined working conditions.

For test 1, in the vessel, during operation, no liquid containing promoter content is added. The test was performed to establish a basis for comparison with tests in which the method according to the present invention was used. A sample of 500 g of consumed catalyst was introduced into the vessel and it was fluidized with nitrogen at the bottom of the vessel, while the system was heated to a temperature of 593^CC. At a specified time, nitrogen was replaced by air, thereby initiating the oxidation of the coke. The exhaust gas from the vessel has carbon oxide concentrations determined by means of the chromatographic apparatus, at different time intervals, after the introduction of air, as shown in table 1.

Table 1 test 1 in the station-piper regeneration area

Without CO oxidation promoter CO concentrations in exhaust gas

<td>Time minutes</td><td>percentages CO in dry smoke gas</td><td>Report CO_?/ CO</td>

<td> 1</td><td> 2,4</td><td> 3,09</td>

<td> 2</td><td> 3,5</td><td> 3,00</td>

<td> 3</td><td> 5,0</td><td> 2,86</td>

<td> 4</td><td> 6,0</td><td> 2,58</td>

<td> 5</td><td> 5,7</td><td> 2,96</td>

As shown in the table, the COi / CO ratio during the test remained within the narrow range of

2.5 to 3.0. test 2 was performed in the same manner as test 1, except that 15 s after allowing the fluidization nitrogen to leak into the air and while increasing the concentration of carbon oxide in the vessel, a 30 cm sample was injected.³ dilute solution of chloroplatinic acid (H-PtClc). The solution was prepared by diluting chloroplatinic acid containing -28.6% by weight platinum with distilled water to obtain dilute chloroplatinic acid containing 0.1 mg Pt / cm³, This amount of chloroplatinic acid corresponds to 6.0 ppm by weight of the catalyst sample in the form of metallic platinum. Chromatographic records show that the concentration of carbon oxide was not reduced. If the test was continued, the exhaust gas shows the composition of table 2.

Table 2

Test 2 with regeneration zone in the pilot station

Diluted chloroplatinic acid (0.1 mg Pt / cm³

Concentration of carbon dioxide in the exhaust gas it

Table 3

Test 3 in the regeneration area at the pilot station

Diluted chloroplatinic acid (0.01 mg Pt / cm³ Concentrations of carbon dioxide in exhaust gas

<td>Time, minutes</td><td>% CO in dry exhaust gas</td><td>Report CO₂/ CO</td>

<td> 1</td><td> 1,7</td><td> 9,3</td>

<td> 2</td><td> &lt;0,1</td><td> &gt; 100</td>

<td> 3</td><td> &lt;0,1</td><td> &gt; 100</td>

<td>Time, minutes</td><td>% CO in dry exhaust gas</td><td>Report CO₂/ CO</td>

<td> 1</td><td> 0,6</td><td> 20,8</td>

<td> 2</td><td> &lt;0,1</td><td> &gt; 100</td>

<td> 3</td><td> &lt;0,1</td><td> &gt; 100</td>

Carbon oxide concentrations are much lower and the COi / CO ratios are much higher than those in test 1 for the same time intervals. In order to experience now how quickly platinum loses its efficiency in reducing the concentration of carbon oxide, the regenerated catalyst from test 2 was used in additional cycles in a hydrocarbon reaction zone in the pilot station and then in the regeneration zone, without the addition of promoter, After the first three additional cycles, through the hydrocarbon reaction zone and the regeneration zone, no carbon oxide formation was observed, when the coke was burnt, but starting with the fourth cycle, a small amount of carbon oxide appeared in the exhaust gas, although this amount was considerably smaller than that in test 1, when no promoter was used,

The same working method was used, using q new sample of catalyst of 5Q0 g for test 3, except that a more dilute solution was used and the liquid containing the promoter was added to the vessel before letting the fluidization nitrogen into the air. , in this test, 25 cm were added to the vessel³ more dilute chloroplatinic acid, corresponding to 0.5 ppm by weight of the catalyst, as metal platinum. The solution was prepared / by diluting a portion of the solution used for test 2, containing 0.1 mg Pt / cm³ with distilled water to obtain a more dilute solution of chloroplatinic acid containing 0.01 mg. ., Pl / cm³. -Cdncentration \ them oxide. car-bon ··· in / the exhaust gas results from &lt;&lt; -; ·^f Table 3 /,. '

Although the reduced amount of promoter used in this assay gives results comparable to those obtained with a higher concentration of promoter in test 2, the regenerated catalyst results in a greater loss of its promoter efficiency and very quickly, as it turns out. from the subsequent cycles that indicate the presence of some carbon oxide during the regeneration phase. After three cycles, it turns out that the catalyst gives about two thirds of the amount of carbon oxide produced during test 1, when no promoter was added.

in test 4, 25 cm³ of a solution of chloropaladic acid in water, · containing 0.1 mg Pd / cm³, corresponding to 5 ppm by weight of the catalyst sample as palladium metal, were injected into. vessel 15 s after the fluidization nitrogen was allowed to escape into the air, thereby starting the combustion. within 2 min, the carbon dioxide concentration in the exhaust gas decreased to less than O, 2o /₀ in volume.

Example 2. In this example the behavior of a regeneration zone in a fluidized catalytic cracking process is described, on an industrial scale, shortly after the addition of small amounts of a liquid containing a carbon oxide oxidation promoter, by the method, according to the present invention, without any other operational changes being made. .

The plant processed, from a mixture of vacuum diesel and coke oil, and presented a quantity of catalyst in circulation of - 601 (54 468kg), catalyst containing 'zeolite. The unit was allowed to 'operate' under typical working conditions, without attempting partial or full reduction; it takes the concentration of carbon dioxide in the gas. . Escape and 'no' existence&gt; in

The regeneration area of ​​a carbon oxide conversion promoter, in Table 4, is given a series of some of these operating conditions of the process, before the promoter has been added to the regeneration zone. Thereafter, from a cylinder in the regeneration zone, 2.1 of a solution of chloroplatinic acid was introduced into the water, for 2 to 3 minutes, through a valve disposed in the regeneration zone. The diluted chloroplatinic acid solution was prepared by diluting with distilled water up to a volume of 2 1 to 61.4 g concentrated chloroplatinic acid (28.637% by weight platinum). When passing this amount of solution into the regeneration zone, a promoter corresponding to 0.32 ppm by weight of catalyst quantity was added. The regeneration zone reacts almost immediately to this addition of 72500. The concentration of carbon dioxide in the exhaust gas was reduced to half that existing before adding the solution and the temperature in the phase ⁵ density in the regeneration zone increased by 25 ° C above that before adding the solution. There have been no other changes in the functioning of the process, in table 4 there is also a series of working conditions after this first addition of solution, in the regeneration area, a few hours later, a more quantity was added. small solution containing promoter corresponding to 0.13 ppm¹⁵ metal platinum. Except for the addition of the promoter, no other work changes were made in the process. ' Table 4 also gives a series of working conditions after this second addition.

Table 4

Behavior of the regeneration zone in the fluidized bed catalytic cracking installation and addition by the promoter

Working conditions chosen

<td>' Characteristics</td><td>.Slart.</td><td>After the addition of 0.32 ppm by weight, PI</td><td>After addition of 0.13 ppm by weight 'Pt</td>

<td>temperatures ^CC 1 Dense phase regeneration zone</td><td> 655</td><td> 681</td><td> . 713</td>

<td>Phase-diluted regeneration zone</td><td> 661</td><td> '687</td><td> 717</td>

<td>Exhaust gas regeneration area ·</td><td> 667</td><td> 678</td><td> 703</td>

<td>Hydrocarbon reaction zone</td><td> 510</td><td> 511</td><td> 511</td>

<td>Combined Load</td><td> 328</td><td> 328</td><td> 329 -</td>

<td>The composition of the exhaust gas, % in you. CO. .</td><td> 10,5</td><td> 5,9</td><td> 1,4</td>

<td>COJ</td><td> 10,8</td><td> 12,8</td><td> 17,1</td>

<td>a₂</td><td> 0,0</td><td> 0,0</td><td> 0,0 -</td>

<td>CO2 / CO</td><td> 1,03</td><td> 2,17 .</td><td> 12,2</td>

<td>Residual carbon on regenerated catalyst,% by weight</td><td> 0,30</td><td> 0,16</td><td> -0,06</td>

<td>Fresh batch ration, rn³/ h</td><td> 124</td><td> 124</td><td> 124</td>

<td>Recycle ration, m³/ h,</td><td> 11</td><td> 11</td><td> 11</td>

<td>Air ration, m³/ s</td><td> 15</td><td> 15</td><td> 15</td>

As shown in the data in Table 4, the carbon dioxide concentration in the exhaust gas decreases by 10.5% by volume. before adding promoter solution to 5.9% by volume, after adding the first solution amount (0.32 ppm by weight) to 1.4% in vo25 world after adding the second solution quantity (0.13 ppm by weight platinum). Carbon on the regenerated catalyst decreases from 0.30% by weight, to 0.16% by weight, after the first solution is added, and then by 0.06% by weight, after adding

<img file="RO72500A_D0001.tif" />

<img file="RO72500A_D0002.tif" />

<img file="RO72500A_D0003.tif" />

of the second solution quantity, while the dense phase temperature in the regeneration zone increases from 655 to 681 ° C and to 713 ° C, after adding the respective solution quantities. .Other^stemperatures in the regeneration zone also increase, but not as much as the temperature in the dense phase.

Example 3. Before adding the two quantities of promoter solution, as described in example 2, an almost complete test was performed. Test 1, for comparison with the following tests to be performed 15, after addition to the promoter solution regeneration area. In the manner described above in Example 2, during the day following the addition of the first two amounts of 20 promoter solution, two larger amounts of promoter solution were added, containing promoter corresponding respectively to 0.13 and 0.32 ppm by weight of the amount of catalyst, as a metallic platinum. During this time, however, the air ration for the regeneration zone was increased to provide sufficient oxygen for the complete conversion of carbon oxide to carbon dioxide. During continuous operation, when the carbon oxide burned completely in the regeneration zone, in the presence of the mixture of carbon oxide conversion promoter and regenerated catalyst, test 2 was performed. During test 2, to the total amount of dilute chloroplatinic acid, which passed into the regeneration zone, carbon oxide oxidation promoter, corresponding to 0.9 ppm by weight of the amount of catalyst as metallic platinum, was added. test 2 was performed with the same feed ratio, the same pressures in the regeneration zone and in the hydrocarbon reaction zone, as those for test 1. No tests were performed prior to the start of test 2 to achieve the same level of conversion as that of test 1, and no attempt was made to optimize the air flow ratio required for complete conversion of carbon oxide. The results for test 1 and test 2 are given in table 5.

Tables 5

Comparative results before and after adding CO conversion promoter

<img file="RO72500A_D0004.tif" />

<td>trying</td><td>1 before</td><td>2 after</td>

<td>Processing conditions Hydrocarbon reaction zone Temperature, ^cC</td><td> 510</td><td> 505</td>

<td>Combined batch temperature, ^CC</td><td> 328</td><td> 313</td>

<td>Regeneration area Dense phase temperature, ° C</td><td> 656</td><td> 696</td>

<td>Diluted phase temperature, ^cC</td><td> 661</td><td> 699</td>

<td>Exhaust gas temperature, ^CC</td><td> 667</td><td> 710</td>

<td>Carbon on regenerated catalyst, % by weight</td><td> 0,28</td><td> 0,11</td>

<td>Exhaust gas analysis,% in you. CO₂</td><td> 10,5</td><td> 14,1</td>

<td>CO</td><td> 9,6</td><td> &lt; 0,1</td>

<td>sheep</td><td> 0,0</td><td> 3,5</td>

<td>CO₂/ CO</td><td> 1,09</td><td> &gt;140</td>

<td>Product efficiency C₂ and lighter. % in rakes</td><td> 2,7</td><td> 2,4</td>

<td>Propylene,% by volume</td><td> 8,5</td><td> 8,2</td>

<td>Propane,% in you</td><td> 2,5</td><td> 2,5</td>

<td>Isobutart,% in you</td><td> 6,1</td><td> 5,5</td>

<td>N-butane,% in you</td><td> 1,7</td><td> 1,6 .</td>

<td>butene_r 'S&gt; /_e in you</td><td> 9,1</td><td> 9,2</td>

<td>C₃ 4- gasoline,% in you</td><td> . 57,6</td><td> 57,4</td>

<td>Easy cycle fraction,% in you '. ''</td><td> 20,1</td><td> 21,2</td>

<td>Residual fraction,% in you</td><td> 3,1</td><td> 3,8</td>

<td>Cokes,% by weight</td><td> * 5,4</td><td> 4,3</td>

<td>Conversion,% in you.</td><td> 79,7</td><td> 78,0</td>

<img file="RO72500A_D0005.tif" />

I.

• 72500 comparison of the test results shows the reduction of the carbon dioxide concentration in the exhaust gas from 10.5% by volume &lt;0.1% by volume, a reduction of the carbon on the regenerated catalyst by 0.28% by weight 0,11% by weight (indicating a better regeneration of the catalyst) and an increase of the temperatures in the regeneration zone from 38 to 44 ° C. Although the temperatures in the hydrocarbon reaction zone are not exactly the same, recovering some of the carbon dioxide combustion heat in the regeneration zone in test 2 allowed a reduction in the combined charge temperature. Although the conversion from test 2 is 1.7% lower than that from test 1, a comparison of yields indicates that for test 2 a more selective crack was obtained for more valuable products than for test 1. The yield of coke for test 2 was 4.3o / ((in weight, compared to 5.4% by weight for test 1 and even if the conversion was l, 7e / o lower for test 2 than for test) 1, the gasoline yield from test 2. was 57.4% by volume, compared to 57.6% by volume for test 1. Subsequent tests on the same industrial unit showed that the complete conversion of carbon oxide can be maintained by passing through the regeneration zone, daily, of promoter solution quantities containing promoter 0.12 (ppm by weight as metal platinum.

Platinum analysis of the catalyst samples from this industrial unit indicates that a noticeable part of the promoter was retained on the crack catalyst. As an example, while in this industrial unit a total amount of chl oroplatinic acid solution was added, containing a total amount of promoter corresponding to 75 g platinum, from the unit a sample of equilibrium catalyst was extracted and the concentration was analyzed. platinum. The value determined for this sample was 1.0 ppm by weight 'platinum, If all 75 g of platinum were passed into the unit and spread equally - 60 t (54 468 kg) quantity would lj could expect a concentration of 1.4 ppm platinum weight on the equilibrium catalyst.

Example 4. This example generally presents the problem of 'chemical instability of the solution, specifically, illustrates the chemical instability of a solution of chloroplatinic acid in a mixture of water and a common freezing point lowering agent. water, ethylene glycol. The chloroplatinic acid, containing 25.46% by weight platinum, is dissolved in a mixture of 1: -l by weight ethylene glycol] and distilled water and separately in tap water, to obtain two solutions containing each 0.045% by weight platinum. These two solutions are analyzed for solubility characteristics at —29^?C and with regard to thermal stability at 22, 43 and 63 C. The data in table 6 show that the solutions are fluid at -29 ° C, but they do not have the desired chemical stability for 30 days at 63 ° C. in 11 days, at, 22^:C, a black precipitate is formed and in only 0.7 days at 63'C. The black precipitate is separated by centrifugation, washed with water^:and it is analyzed with regard to the platinum content: platinum content. elementary of the black precipitate is found to be 94% and the chemical analysis of mainly metallic platinum spectroscopy with 5% PtO.

These data indicate that the black precipitate is Pt °, suggesting a reduction of Pt⁺⁴of chloroplatinic acid at Pt ° and oxidation of ethylene glycol. The oxidation products of ethylene glycol have not been identified.

Table 6

The stability of chloroplatinic acid in ethylene glycol and water

<td rowspan="2">Sample</td><td rowspan="2">Type of water</td><td colspan="4">Days of precipitate formation</td>

<td> —29^CC.</td><td>22 ° C</td><td>43 ° C</td><td>63 ° C</td>

<td> 7 1</td><td>Forgotten</td><td>soluble</td><td> ~ 11</td><td> 4</td><td> 0,7</td>

<td> 2</td><td>tap,</td><td>soluble</td><td> 11</td><td> 0,7</td><td> 0,7</td>

. leashes at -30, 22 and 63 ° C for 10 hours • Chloroplatinic acid (CPA) ions, in a concentration corresponding to 0.045% in

Example 5. · This example shows the freezing point data and ¹ A 'stahilițatejichijhipă,; at '' - '' Temperatures

Â ί A '\ 1'

Λ, .ίΐ.2. * V. '-'. ...

<img file="RO72500A_D0006.tif" />

) 5 weight platinum in different primary, secondary or tertiary alcohols of pure quality or mixtures thereof. A temperature of -36 ° C was chosen to simulate the lowest temperature that can be encountered in the range; the temperature of 22 ° C was chosen to simulate ambient conditions and 63^CC was chosen to simulate average storage conditions (indoor and outdoor). The days were noted until the appearance of a black precipitate, most probably Pt °, for each temperature. The data are shown in Table 7.

Table 7

Stability of the CPA¹· In different soil due to different temperatures

<td rowspan="2">Solu- tion no.</td><td colspan="4">Solvent</td><td colspan="3">Days of precipitate formation</td>

<td colspan="2">the top sections, Type _OCL</td><td colspan="2">hot item FP oc¹ "C¹</td><td colspan="2">- 36 ° C j 22^cC</td><td>63 ° C</td>

<td> 1</td><td>methanol</td><td> — 97</td><td rowspan="2"> 65 78</td><td> 12</td><td colspan="2"> ND 3 1 14</td><td> 0,25</td>

<td rowspan="8"> 2 3 4 5 6 7 8 . 9</td><td>ethanol</td><td rowspan="2"> — 112 -- 127</td><td> 12</td><td>Liquid</td><td rowspan="2"> &gt;61 &gt; 61</td><td> 44</td>

<td>1-Propanol</td><td> 98</td><td rowspan="2"> 16—29 12—16</td><td>Liquid</td><td> &gt; 58</td>

<td>2-Propanol</td><td rowspan="2"> — 85 — 89</td><td rowspan="2"> 83 117</td><td>ND</td><td> 7</td><td> 1</td>

<td>1-But an ol</td><td> 37 -</td><td>Liquid</td><td> &gt; 63</td><td> 50</td>

<td>2-Butanol</td><td> — 89</td><td> 100</td><td> 24</td><td>ND</td><td> 56'</td><td rowspan="2"> 2 13</td>

<td>2-Melyl-2-propane</td><td> 25</td><td rowspan="2"> 83 157</td><td>II</td><td>Solid</td><td> 22</td>

<td>1-hexanol</td><td> — 51</td><td> 74</td><td>Liquid</td><td> &gt; 56</td><td> 42</td>

<td>2-ethyl-l-hexanol</td><td> — 70</td><td> 184</td><td> 85 </td><td> &gt; 60</td><td> &gt; 60</td><td> &gt; 60</td>

<td>to</td><td>Ethanol + jb 1-Butanol '&gt; HA)</td><td></td><td></td><td></td><td>ND</td><td> &gt; 48</td><td> &gt; 48</td>

1) Values ​​in the literature for melting point (top section), boiling point (boiling point), flash point (F.PJ.

2) Flash point,

3) ND = determine C, V

4) CPA concentration in each solution corresponding to 0.045% by weight platinum.

The chemical stability of chloroplatinic acid is the highest. good for aliphatic alcohols ''. saturated primaries (except methyl alcohol) and weaker for saturated secondary and tertiary aliphatic alcohols, except that it is inappropriate due to poor chemical stability, CPA-2-methyl-2-propanol solution is solid at -36 ° C. A number of CPA solutions in different solvents, in order of decreasing chemical stability to 63^CC are; 2-ethyl-1-hexanol (greater than 60 days)_; 1-propanol (over 58 days); 1-butanol (50 days); ethanol and 1-hexanol (42 ... 44 days); 2-methyl-2-propanol (13 days); 2-propanol and 2-butanol (1... 2 days); and methanol (0.25 days).

Example 6. This example describes the tests in the regeneration zone at the pilot station, which were performed to determine the efficiency of a solution containing 1-butanol chloroplastic acid to reduce the carbon dioxide concentration in the exhaust gas. try: the countries were executed using the work equipment described in Example 1. As in e20 xempiu 1, the apparatus was heated to a constant temperature and chromatographic apparatus was used for continuous sampling and analysis of the exhaust gas from. vessel on carbon oxide, carbon dioxide and oxygen. Chromatographic traces of parbon oxide, bi-, carbon dioxide and oxygen were determined as a result of the moment analyzes for the characterization of carbon oxide combustion. during the test. From the chromatographic traces of each test, a specific ratio CO / CO was calculated, considered as the minimum ratio COa / CO, by first determining the maximum concentration of carbon oxide for the test (which usually takes place in 2.) 3- min after the initiation of combustion), determining the concentration of carbon dioxide at the maximum concentration of oxide. carbon, and then calculating the COa / CO ratio for the concentrations thus determined. The report is considered as the minimum COz / CO ratio, as it has been observed from several such regeneration attempts; that if · they were in '? - YOU

..

recorded CCh / CO ratios from moment to time elapsed in each test, will result in a curve that will pass through a minimum CCL / CO ratio having a value calculated by the method described above. It was found that this minimum CCU / CO ratio best characterizes the performance of any solution containing a carbon oxide promoter when catalyzing carbon oxide combustion.

The tests were performed on samples of 500 g of catalyst containing zeolite, which was "first consumed by passing diesel over the catalyst sample in a hydrocarbon reaction zone, in a pilot station, which was allowed to operate under conditions. standard. Each sample of catalyst consumed had 0, Qo /₀by weight coke.

In test 1 no solution containing promoter content was used, the test was performed to establish a basis for comparison with a subsequent test, in which a solution with promoter content was used. A sample of 500 g of consumed catalyst was introduced into the vessel and fluidized with nitrogen, entering the bottom of the vessel, while the system was heated to a temperature of 593 ° C. at a given time, nitrogen was replaced by air, thereby initiating the oxidation of the coke. The exhaust gas from the vessel was analyzed with respect to carbon dioxide, carbon oxide and oxygen, using a chromatography apparatus and from the traces of carbon dioxide and carbon oxide the minimum COa / CO ratio was calculated. In order to determine the reproducibility of the results obtained with the test method, the test was repeated with separate samples of the consumed catalyst, ie four times. The minimum CCL / CO ratios are between 2.5 and 3.3 and are given in table 8.

Test 2 was performed in the same manner as test 1, except that, before allowing the fluidization nitrogen to escape into the air, a 25 g sample of a solution of chloroplatinic acid was injected into the regeneration zone. 1-butanol. The chloroplatinic acid concentration in the sample corresponded to 0.008¾ by weight platinum and the amount of platinum in the sample was 2 mq platinum or 4 ppm by weight of the 500 q catalyst sample. A minimum CCb / CO ratio of 52.1 resulted and then to obtain a ration size at which the mixture of promoter particles and regenerated catalyst particles loses efficiency to reduce the carbon dioxide concentration in the exhaust gas, the mixture is passed through several cycles, specifically, to complete another cycle, the mixture was "consumed in the hydrocarbon reaction zone at the pilot station, as described above, and the test in the regeneration zone was repeated, but without adding any additional amounts of promoter solution. At the end of the seventh cycle, the minimum CCb / CO ratio for the mixture was 41.5, indicating that the mixture retained and retained most of its action of burning carbon oxide. The results for test 1 and test 2 are given in table 8.

Table 8 tests in the regeneration area in the pilot station with and again the use of a promoter solution

<td rowspan="2">Cycle</td><td colspan="7">Minimum C0 ratios₂/ CO</td>

<td> 1</td><td> 2</td><td> 3</td><td> '4</td><td> 5</td><td> 6</td><td> 7</td>

<td>Attempt 1 (not to be used by a promoter)</td><td> 3,3 2,5 3.1 3,0</td><td> —</td><td> —</td><td> —</td><td> —</td><td> —</td><td> —</td>

<td>test 2 (25 g CPA-1-bulanol solution, containing 0.008% by weight platinum)</td><td> 52,1</td><td></td><td> -</td><td></td><td> -</td><td></td><td> 41,5</td>

of carbon oxide, obtained in reactions. «litigation

The process according to the invention has the advantage of regenerating a catalyst impurized with coke, simultaneously with the controlled combustion of recovering heat

CPA solutions in other preferred students are expected to exhibit behavior similar to that of the solution.

GPA in 1-butanol used in this external exam and reusing it in the regeneration area.