专利摘要:
A process is disclosed for the regeneration of a solid metal phthalocyanine catalyst bed system which comprises a metal phthalocyanine impregnated on a charcoal support, said regeneration comprising (a) washing said charcoal support with water at a temperature of about 200 DEG F. to about 350 DEG F. to extract excess caustic and hydrocarbonaceous materials, (b) treating the washed charcoal support with steam at a temperature of about 650 DEG F. to about 1000 DEG F. and (c) reimpregnating the treated charcoal support with from about 0.001 wt. % to about 10.00 wt. % of a metal phthalocyanine compound.
公开号:SU860680A1
申请号:SU762388801
申请日:1976-08-17
公开日:1981-08-30
发明作者:Хилфман Ли
申请人:Юопинк (Фирма);
IPC主号:
专利说明:

; 54) METHOD FOR REGENERATION OF CATALYST FOR CONVERSION MERCAPTAN invention relates to a catalyst regeneration methods for the conversion of mercaptans contained in petroleum distillates consisting of carbon carrier impregnated FTA lotsianinkobaltom and deactivated during the processing of petroleum distillates caustic soda and Kis lorodom or by air. A known method for the regeneration of phthalo cyanine-added catalyst for the conversion of mercptanes contained in petroleum distillates by treating the catalyst with water and / or water vapor at a temperature above, preferably at 82 ° C for 2-48 hours, followed by impregnation with a solution of phthalocyanine compound Til The closest To the proposed technical essence and achievable effect is the method of catalyst regeneration for the conversion of mercaptans contained in petroleum. distillates consisting of carbon carrier impregnated with phthalocyanine cobalt and deactivated during the treatment of petroleum distillates with caustic soda and oxygen or air by washing the catalyst with boiling water, acetic acid, boiling water followed by treatment with superheated steam at a temperature not and .215, C, and phthalocyanine cobalt impregnation with monosulfonate to a content of 0.00110, 0 wt.% 2. The disadvantages of this method are the low degree of regeneration, since it allows to achieve a regenerative catalyst activity equal to 52% of the original. . The purpose of the invention is to increase the degree of regeneration. This goal is achieved by the fact that in the method of catalyst regeneration for the conversion of mercaptans contained in petroleum distillates, consisting of carbon carrier impregnated with phthalocyanine cobalt and deactivated during the processing of petroleum distillates with caustic soda and oxygen or air, by flushing the catalyst with a boil with boiling water, acetic acid, repeated boiling water with subsequent treatment with superheated steam and impregnation with phthalocyanine cobalt monosulfonate to a content of 0.001 to 10.0 wt.%, processed HH-H :.
c; -iiB 2CiHt.ui, u 3 nachn gsl jjio TON p: ir4M-:; pi) aHM and dos I1 adst peiaHcp.jpOriaHKOro atali a.ooa; iiOii 931: Ol: Ermocacha Y1Oh
The present invention relates to the method of regeneration of catalp-bicuspid CHCTe ifci. consisting of a crotch r .o, c-dolgki, propltaknoy MeTa; ijienr.) On3Bo, nFi; j phtalodiancn. First stage r; rhodssa rzgenerats
with YT, e with t n l; - ;. m tl P; : LOGICS. FOOD IlpH mywcon coal
by.
; 7 ° C) l; l skstra2 C O - 3 5 O F (S 3, 3
Coal iodine gironani Ogtsilo ;; in h X i 1 p om; n to and .. MaTepriaiTOD at .Which water: a cat is present; BOjjacb JJ as PC ;;; eslk processing of Bsdets B of the interval of the INDICATORS at the OLD
noflj: o; xKM). Conditions;
yomom ;; j k l in to a-; hall 1 1 00 a / l; -4. are; ia; iJieHKe in hiirej.
rasa, for example, Ge Pomopd KKefJTHoro Gs 5.gnert;
LKE IL; - Z. ZOT, to I1
rtij-pv -; not used
; av gsvl - but nk; -; e: ;; gnog-o
jj (OpopP-bix mater ;; -a.lov, zloch ;;:; to yivjeBO blend materials; -; get rid of the coal layer when rinsing it with water .. the pH of the washing system can be used as an indicator of the amount of caustic and hydrocarbons removed from solid substrate, preferably pp should be below 9 to ensure that excess caustic is removed to hydrocarbons, during the washing process, from dilute carboxylic acid solution, due to which the washing system pK can be reduced to 7, however, carboxylic acid should be removed from coal floor systems and with the aid of p-precipitating rinsing with water. RELATING to the corresponding carboxylic acids; formic, acetic, propionic, and others. The washed coal is then treated with steam at 650–850 ° F (343.3–454.4 ° C) under the processing conditions. Processing conditions include a pressure of 1-100 atm, which can also be carried out by the presence of an inert gas, such as nitrogen, gels or argon. The inert gas can be used not only as a diluent, but also as a carrier to remove any free-floating heavy oils, distilled with coal as a result of processing it with superheated steam at 650-850 ° F. Steam treatment is carried out at approximately 0.010 pounds of steam per pound of catalyst per hour to 0.800 pounds of steam per pound of catalyst per hour (the same ratios in the metric system). From economic considerations it is advisable to spend the minimum amount of steam. Ganna coal in new propioct & i.e. conditions; propi-gm1lani, 1, complex 75-100 ° F (23.9-37.8 ° C) and donation 1-100: 1 is recommended: th way KOKGf 6; -ltt imposes what kind of new impregnation of a solid carbon substrate metal phthalociai-ji-n-ia, although not necessarily with an equivalent result. A new impregnation of the base layer is carried out in any way, using an old-fashioned method, the carbon substrate treated with superheated steam removes the residual metal derivative phthal-O thia; A new pro-pit of processed coal underfloor / c-ki1.1aet the amount of metallo-pdnogo phthalociain in, which appeared after the processing of p-arom.
Solid carbon carrier substrate can be obtained from coal obtained, for example, by destructive distilling of wood, peat, drill coal, bituminous shale, bone coal, vegetable or other carbonaceous materials, for example,; Glen Nispag, produced by Westvaco, derived from plant sources, such as chopped wood pulp, Hydrodarco (known as DARCO), produced by the company, Atlas Chemical Room, H-Orit coal, produced by Norit, derived from peat, Columbi Carbon, special coal, produced Pittsburgh Coal - from brown coal produced by Calgon Comp. The metal-sponge phthalodianines used to re-impregnate the treated carbon substrate, for example, sulfonates or carboxylate metal phthalocyanine, for example phthalocyanine cobalt. The regenerated carbon substrate impregnated with phthalocyanine metal derivative can be used in the conversion of mercaptans containing compounds in petroleum distillate. Mercaptan-containing compounds may contain 1-19 carbon atoms. Other mercaptan derivatives that may be contained in a distillate include aromatic mercaptans like thiophenol or substituted thiophenol, or branched-chain aliphatic, difficult-to-process mercaptans like tert-dodecylmercapt Specific types of mercaptans that can be converted to disulfides using a -regenerated catalytic system (in the solid layer) include methyl mercaptans, ethyl mercaptan, propyl mercaptan, and others. Treatment of micro-containing compounds in the presence of reducing impregnation .-; In the alkaline medium, for example, sodium hydroxide, caustic potash, edonicolite, rubidium hydroxide, cesium hydroxide, or other suitable alkaline materials, including the corresponding chyme chyme, cheskone hydroxide or other suitable alkaline materials, including the corresponding chyme, cesium hydroxide or other suitable alkaline materials. quaternary ammonium.
Example 1. Coal (Norit RCDA) as indicated in table. 1, impregnated with 150 mg of phthalociacnocobalt monosulphonate and continuously used to convert mercaptan derivatives to disulfide until a melting oil is accumulated on the surface of the carbon substrate.
Table 1
Bulk weight, g / cm Calcium (according to AA5), wt.,%
Magnesium (by AAS), wt.%
Emissicon-spectrographic a: yliz, wt.% Metal:; The used impregnated carbon is moistened with 5 ml of sodium hydroxide with a strength of 50 10 ° Be and is introduced into a glass containing 100 ml of sulfur distillate and kerosene, which has the following physical properties (see, Table 2). Table 2 55 Hydrogen sulphide, ppt2 Mercaptan sulfur, ppt390 Copper, mg / l0,021 Acidic y-SO. Lo, ml con / g 0.001 Color according to Saybold 30 Distil qi: Beginning of boiling, Of 349 (176,) 5364 (184,) 65
j C) -} -, -: C; (End of boiling ° F 490 and 54)
S
The acid number is determined by titration with caustic potassium.
Sekbold Tseet is determined after 20 hours of acceleration.
Kerosene is agitated with the used impregnated: metal derivative; phthalocyanine with the addition of air in the presence of air at a pressure and temperature around the environment. Samples of kerosene are periodically sampled, and the anal1 is filtered: air from the sulfur mercaptan content.
The results of the analysis are presented in table. 3
Table 3
Mercaptan sulfur, weight. ppt
388
81 45 33
30 - 60
90 120 From tab. 3, it can be seen that the kerosene to be treated contains 81% o of mercaptan sulfur after 30 minutes and 33% o after 90 minutes. Coal (Norit) is removed from the beaker and treated with water at 212 F (100 ° C) and 1 atm for the time required to lower the pH of the coal layer to 9. The layer is treated with hot diluted acetic acid, adjusted to pH 7, and then boiled water to remove excess acetic acid. The coal (Norit) is then treated with steam at 850 ° F (454.4 ° C) for 3 hours at a rate of 4 mol / h of steam and dried under ambient conditions. The steam-treated layer is transferred to a second beaker containing 5 ml of caustic soda with Yu Be strength plus 100 ml of distillate kerosene according to the composition shown in Table. 2. Kerosene is shaken with a re-impregnated carbon substrate in the presence of air at ambient temperature and pressure. Kerosene samples are taken periodically, filtered and analyzed for the content of mercaptan sulfur. The results of the analysis are presented in table. 4. Table 4 Continue to shake your Mercaptan sensibility, weight. ppto waE {and, min. The second portion of the carbon layer treated with steam is impregnated again using the known impregnation method with fresh (catalyst) phthalocyanine cobalt monosulfonate to such a degree that the substrate contains 150 m of phthalocyanine cobalt 100 cm of Norit coal. The newly impregnated catalytic substrate is wetted again with caustic soda and added to 100 ml of sulfurous kerosene distillate (composition - Table 2). Kerosene is again continuously shaken with a substrate soaked in a catalyst in the presence of air at ambient temperature and pressure. Samples of kerosene are taken periodically and filtered and analyzed for the content of mercaptan sulfur. The results of the analysis are given in table. 5. Table b. Continued Mercaptan with shaken weight, wt. ppm vani, min. Analysis of the results given in table. 3-5, shows that, in Table 3 of the Mev1captan-Containing Source, the raw materials are treated with depleted or significantly weakened coal impregnated with phthalocyanine metal. The content of mercapt (mercaptan sulfur) is 81 ppm in 30 minutes and 33 ppm in 90 minutes. In contrast table. 3. | | tab. 4 shows that the treated steam, not subjected to a new impregnation (previously impregnated) with a metal derivative phta locyanin, the carbon substrate gives 29 ppm (weight) mercaptan sulfur after 30 min and 11 ppm after 90 min. The result is given in table. 5, obtained using the proposed method of regeneration of depleted coal (Norit), as shown in the table. 3. Soder / Kaniya mercaptan sulfur (in weight. Ppm) in the table. 5 after 30 minutes 12 ppm, and after 90 minutes only 4 ppm. This table shows a decrease from 81 ppm after 30 minutes (Table 3) to 12 ppm after 30 minutes. (Table 5) after using the proposed regeneration method. Thus, the result is shown in obtaining only 4 ppm of mercaptan sulfur using the proposed regeneration method, as opposed to 33 ppm of mercaptan sulfur Res. Example 2. Hydrodarko carbon impregnated with 150 mg of phthalocyanine cobalt monosulfonate per 100 cm of coal was used, which was moistened with 5 ml of caustic soda Yu Be and added to 100 ml of sulfurous kerosene distillate, as indicated in table. 2. Kerosene is agitated with a substrate with a depleted catalyst in the presence of air at ambient temperature and pressure. Samples of kerosene are taken periodically, filtered and analyzed for the content of mercaptan sulfur. The results of the analysis are given in table. 6, Table 6 Continued Mercaptan Sentiment shaken up, weight. rt vani, min Remove the impregnated carbon layer (Hydrodarco) and wash with boiling water to pH 9, dilute with acetic acid to pH 7 and finally boil with water at 212 (100 ° C) to remove residual acetic acid. The washed coal layer is treated with steam at, (454.4 ° C) for 3 hours at a rate of 4 mol / h. The washed and treated catalytic system is tested on 100 ml of kerosene (the composition specified in example 2), shaken, the test results are presented in Table. 7, Table Continued Mercaptan Shake Size, wt. The results given in Table 7 show that the carbon substrate not impregnated reduces the mercaptan content to 124 ppm of me- ctan sulfur in 30 minutes compared to 23 ppm of mercaptan sulfur in the same time. catalytic system and steam treated. After 120 min of treatment, using a depleted catalyst, the content {by weight. ppm) of mercaptan sulfur reaches 54, in contrast to 4f reached by Autym using a washed, processed, and non-reinfused catalytic system. A part of the washed and steamed catalytic system is further impregnated (reimpregnated) with fresh phthalocyanine cobalt monosulfonate so that the coal substrate contains 150 mg of phthalocyanine cobalt monosulfonate per 100 cm of coal (Hydrodarko). The test results of the newly soaked, washed and treated catcher are given in table. 8. Table 81202 ie t abl. 8 BTurHO, that again the propane catalytic system further reduces the content of mercaptan (23 pp in table 7 after 30 minutes against 10 ppm after 30 minutes in table 8) and significantly reduces the content of mercaptan in table. b, using the exhausted system (with Hydrodarko coal). In tab. b, after 30 minutes of treatment, the content of mercapt sulfur (in weight) was 124 compared to 10 obtained with the use of washed, steamed, and reimpregnated catalyst ns tgbl. 8. Weight reduction. The ppm of mercaptan sulfur is 30 times more than 10 times, and this ratio is maintained for 120 minutes during the treatment of the mercaptan containing kerosene distillate. Example 3. This example shows the inadequacy of the treatment of a deactivated catalyst by a low-temperature oil refining vapor, which is usually at a temperature of up to 215 ° C, i.e. according to a known method. In each of the following comparative tests, 100 cm of an industrial carbon catalyst impregnated with cobalt phthalocyanine again monosulpha-. The phonate, previously deactivated during the processing of the fire resistant mercaptan kerosene distillate and subjected to regeneration steam treatment, is shaken together with 100 ml of the indicated kerosene in a glass vessel. The mixture is shaken in contact with air at ambient temperature and pressure. In these tests, kerosene is sampled periodically and analyzed for mercaptan sulfur in units of weight parts per million of mercaptans (ppm). In addition to the temperature of the regeneration treatment with steam, all the samples are processed sequentially in the same way. For example, before the steam regeneration process, the deactivated catalyst is washed first with boiling water at pH 9, then with dilute acetic acid at 6b ° C and pH 7, and finally again with boiling water to remove excess acetic acid. Also, before testing with shaking, the steam regenerated catalyst in each case, moistened with sodium hydroxide solution. One sample of the deactivated catalyst, hereinafter referred to as Catalyst A, is regenerated with steam at 290 F (), slightly above the steam temperature, usually found at the place of oil refining, but within the temperature range indicated by a known method. The steam is passed over the catalyst for one hour at a rate of 4 mol / h. Another sample of deactivated catalyst, hereinafter referred to as catalyst C, is regenerated with steam at 850F (454.4 s) and the steam is passed through for one hour at a rate of 4 mol / hour. Another sample of the deactivated catalyst is regenerated with steam at 290 ° F (), as described with respect to catalyst A. In this case, the steam-regenerated catalyst is again impregnated with cobalt
phthalocyanine monosulfate using an appropriate method to re-establish the level of cobalt phthalocyanine monosulfonate at 150 mg per 100 cm of carbon base. This regenerated steam re-impregnated catalyst is hereinafter referred to as catalyst B.
And another sample of the deactivated catalyst is regenerated with steam at (454 ° C), as described in relation to catalyst C, and then the regenerated catalyst is again impregnated by re-establishing the level of cobalt phthalocyanine monosulfonate to 150 mg per 100 ml of carbon base. This catalyst is hereinafter referred to as catalyst D.
In order to give ycTaHOBijTb the minimum temperature of regeneration steam, at which the proposed method effectively leads to a hollow result of steam treatment, catalyst G is treated with superheated steam at
650 ° F (343 ° C) for 5 h at a pressure of 34.5 atm. Next, the regenerated catalyst is again impregnated with cobalt phthalocyanine mono-sulfate to ensure the content of 150 mg / 100 ml of coal base, as
previous catalysts have done pax.
The results of the shaking tests are presented in table. 9 for comparison. The results of similar tests of freshly prepared carbon catalyst impregnated with cobalt phthalocyanine monosulfate are also presented in Table. 9 (Catalyst E). This catalyst, with the exception of deactivation, is no different from the same catalysts of previous catalysts, and the shaking test is carried out on it by the proposed method.
This example is presented in order to emphasize the improvement - after regeneration, which is necessary for the practice of the invention.
Table 9 f
权利要求:
Claims (1)
[1]
Claim
A method of regenerating a catalyst for the conversion of mercaptans containing VNIIIP J 3 order 7587/32 contained in petroleum distillates, consisting of a carbon support impregnated with phthalocyanine cobalt and deactivated during the processing of 45 petroleum distillates with caustic soda and oxygen or air, by washing the catalyst with boiling water, repeatedly boiling water, followed by treatment with steam overheated and impregnated with phthalocyanine cobalt monosulfonate to a content of 0.001-10.0 wt.%, characterized in that, in order to increase degree of regeneration, treatment with superheated steam is carried out at 343454 ° C.
类似技术:
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同族专利:
公开号 | 公开日
DE2634991C3|1979-01-25|
DE2634991A1|1977-02-24|
DE2634991B2|1978-03-16|
FR2321329A1|1977-03-18|
ZA764642B|1977-07-27|
JPS5238490A|1977-03-25|
AR228121A1|1983-01-31|
IT1065000B|1985-02-25|
BR7605374A|1977-08-16|
YU40149B|1985-08-31|
US4009120A|1977-02-22|
SE7609158L|1977-02-19|
CA1072526A|1980-02-26|
GB1554315A|1979-10-17|
ES450764A1|1977-08-01|
SE428880B|1983-08-01|
JPS5737378B2|1982-08-09|
DD128522A5|1977-11-23|
YU201376A|1982-05-31|
GR61608B|1978-12-02|
FR2321329B1|1981-09-25|
引用文献:
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法律状态:
优先权:
申请号 | 申请日 | 专利标题
US05/605,798|US4009120A|1975-08-18|1975-08-18|Process for the regeneration of a solid bed metal phthalocyanine catalyst system|
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