SU834108A1 - Method of hydro-purification of liquid products of hydrocarbon pyrolysis - Google Patents

Description

The invention relates to methods for hydrotreating liquid products of the pyrolysis of hydrocarbon feeds from reactive unsaturated compounds with a hydrogenation chain, from which high-quality products are isolated, for example, ~ 5 mer, benzene, toluene, xylene naphthalene.

Known process for hydrotreating pyrolysis liquid products of hydrocarbons by contacting it with the hydrogenation catalysts with the preliminary HA ^'0 grevaniem feed in admixture with hydrogen in the presence of a wood-resin inhibition. Torah.

Wood-inhibitor prevents the resin to some extent obraeova- ¹⁵ of polymeric products and longer catalyst life hydrogenation reaction Tx].

However, during the process obraze- _m vanie polymer products still much used inhibitor is poorly soluble in the feedstock, in the presence of water passes into the aqueous phase and loses its ability to suppress side reactions of polymerization.

Closest to the invention is a method for hydrotreating liquid pyrolysis products of hydrocarbon feedstocks, in particular from unsaturated compounds. A polymerization inhibitor is added to the feedstock, heated to 200-260 ° C together with hydrogen, and the resulting mixture is hydrogenated in the presence of an aluminum-nickel-molybdenum hydrogenation catalyst (2]> Thus, the feedstock is purified from Diene compounds and some sulfur compounds. Ionol is used as a polymerization inhibitor , tolans, technical mixture of alkyl phenols, etc.

The disadvantage of this method lies in the complex process technology, due to the formation of a sufficiently large amount of solid polymers in the apparatus, reduction due to this service life of the used catalyst and the need for laborious work for

7,834,108 removal of polymers and replacement of the catalyst.

The chain of invention is the simplification of process technology.

This goal is achieved by 5, that, in the method of hydrotreating liquid products of the pyrolysis of hydrocarbon feeds from unsaturated compounds by heating the feedstock in the presence of a polymerization inhibitor - phenolic fraction 10 with a boiling point of 180-270 ° C, isolated from wastewater of the semi-coking process, coal, and hydrogen, followed by contacting the resulting mixture with a hydrogenation catalyst, as an inhibitor of the polymerization of the phenolic fraction with a boiling point of 18027О ⁰ С, isolated from semi-effluent coal tapping.

The phenolic fraction of wastewater from the coal semi-coking process 20 contains cresols, xylenols, pyrocatechol, and alkyl catechol, which effectively prevent side reactions.

The method is carried out as follows.

Freshly distilled fractions of the liquid products of the pyrolysis of hydrocarbons, for example gasoline, gas oil, dissolved shale and coal, with a boiling point of 30 to 360 ° C, are inhibited by the phenolic fraction of the wastewater of the coal semi-coking process (hereinafter referred to as the phenolic fraction). The amount of inhibitor used is 0.001-0.5 wt.%. Inhibited feedstock 35 together with hydrogen is heated in a heat exchanger to 50-3 00 ° C and sent to the reactor for contacting with the hydrogenation catalyst of unsaturated compounds. As hydroxypropyl rirovaniya ⁴⁰ catalysts are, for example alyumopal la diysu pfi dny minutes and lyumokoba l tmolibdenovy, alyumonikelmolibdenovy.

The hydrogenation process is carried out in one or more steps. 100-1000 cubic meters of hydrogen are supplied per cubic meter of 45 raw materials. The process pressure is 10-100 atm. The volumetric rate of 0.5-10.0 volumes of raw materials per volume of catalyst per hour. fifty

Example 1. As a raw material, a fraction of the liquid products of pyrolysis of gasoline is used at 35-200 ° C (c | d = 0.835, 11 ^ ^ 1.4760, the bromine number is 65.7, ^{and the} “ ₅₅ new number is 11, 5, the actual resin content is 9.0 mg / 100 mp, the aromatic hydrocarbon content is 75%). The feedstock, together with hydrogen, is heated in a tubular heat exchanger and sent to a reactor for catalytic hydrogenation.

The table shows the effect of the inhibitor used in the proposed method and known on the content of actual resins in the raw material after it is heated in the heat exchanger. The experiment is carried out at a pressure of 15 atmospheres, a space velocity of 1 h ~ at a hydrogen: feed ratio of 200 nm ^ / m.

Inhibitor ^ The amount of inhibitor, wt.% Heating temperature ° C '' actual resins in the product after heating, mg / 100 ml Phenolic fraction 0.005 fifty 10,2 Also 0.005 150 24.0 P 0.01 fifty 9.0 If 0.01 145 10,4 P 0.01 215 1.9.0 tr 0.05 145 12.6 0.05 290 2 9.4 Ionol 0.01 145 14.9 Also 0.01 215 42.0 Resin Wood 0.05 145 26.8 Also 0.05 215 49.5 Without inhibitor ί - 100 167.0 Also "· 200 1000

Example 2. In the raw material according to the example, 0.01 wt.% Of the inhibitor is added — the phenolic fraction, the mixture is heated in a heat exchanger at 180 ° C, a pressure of 50 atm, a space velocity of 3 hours, a ratio of hydrogen-raw materials of 200 nm ^ / m ⁵ and hydrogenated in the same conditions in the presence of apium palladium sulfide catalyst.

The actual resin content in the product after heating in front of the reactor is 15.6 mg /

634108

7100 mp, in the hydrogenate (after the reactor) 1.2 mg / 100 mp.

Example 3. In the feedstock fraction with a boiling point of 70 150 C liquid benzene pyrolysis products, on (dj | ^O -O, 815; Poison -1.518, bromine number 43.8, actual smop content in the freshly distilled fraction 3.8 mg / 100 ml) add a phenolic fraction in an amount of 0.01 wt.%, Heated in a heat exchanger at 145 ° C, a pressure of 40 ata, a hydrogen: feed ratio of 200 nm ^ / m ^ space velocity of 3 h ~ 1. Then, hydrogenation is carried out in the presence of an aluminopaladium-sulphide catalyst in the same conditions. The actual resin content in the feed after heating was 4.1 mg / 100 ml, in the hydrogenate 1.0 mg / 100 mp.

Example 4. In the feedstock, the Su fraction with a boiling point of 2870 ° С of liquid products of atmospheric gas oil pyrolysis (c1д ° 0.7686, lljpl, 4038, bromine number 120, diene content 60 wt.%, Actual resin content in freshly distilled fraction 3, 6 mg / 100 mp). add the phenolic fraction in an amount of 0.02 wt.%, is heated in a heat exchanger at a temperature of 80 ° C, a pressure of 40 ata, the ratio of hydrogen: raw materials 250 mn ^ / m? 30 at a space velocity of 3 hours * ’* and is hydrogenated in the presence of an aluminum-palladium sulfide catalyst under the same conditions. The content of actual resins in the product after heating is 6.4 mg / 100 mp, in hydrogen-35 it is 1.7 mg / 100 mp.

Example 5. In the feedstock fraction with a boiling point of 230 - 32 ° C, the liquid products of the pyrolysis of brown coal (<? D ° ~ 0.96, the bromine number is 44.5, the actual resin content in the freshly distilled fraction is 12.9 mg / 100 mp) add the phenolic fraction in an amount of 0.02 wt.%, heat in a heat exchanger at a temperature of 10 ° C, a pressure of 40 atmospheres, a space velocity of 1.0 h “^, a hydrogen: feed ratio of 400 nm ^E / m 3 _and hydrogenate under the same conditions under the presence of an alum! / - ₅₀ mopalladium-sulphide catalyst. The actual resin content in the hydrogenate is 1.5 mg / 100 ml.

Example 6. (comparative). About · ₅₅ process is carried out under the conditions of example 5, but without the addition of an inhibitor. The used catalyst after 100 hours of operation loses its activity by 60%. The heat exchanger is completely clogged with solid polymers.

Example 7. In the feedstock fraction with a boiling point of 250 5 36 (? C liquid pyrolysis products of A. atmospheric gas oil (d ^? = 0.99, bromine ^ number 35.7, the actual resin content in the freshly distilled fraction 14, Omg / 1OOmp 0.1 wt% of the phenolic fraction is added, 10 ^ is heated at a temperature of 200 ° C, a pressure of 40 ata, a space velocity of 1.5 is the ratio of hydrogen: raw materials is 200 nm ^ / m ^, and it is hydrogenated. '2.7 mg / 100 ml.

Free from diene compounds, the feedstock obtained according to examples 2-7 can be sent to exhaustive hydrotreating from unsaturated and sulfur compounds in the presence of oxide or sulfide hydrotreating catalysts.

Example 8. Ionol in the amount of 0.01 wt.% Is added to the raw materials of Example 1, ί is heated at a temperature of 200 ° C, a pressure of 85 ata, a hydrogen: feed ratio of 800 nm ^ / m ^, a space velocity of 6 h '^ and hydrogenated after 500 hours of operation, the amount of deposited coke on the alumopalpadium sulfide catalyst is 7.3 wt.%.

When using the same raw material with the addition of a phenolic fraction in an amount of 0.007 wt.%, The amount of coke on the catalyst is 4.5 wt.%.

When using the method according to the invention, the amount of polymer products formed is reduced by 2–4 times, the catalyst service life is increased by 10–20%. *

Claims (2)

(54) METHOD FOR FIRING OF LIQUID PRODUCTS OF HYDROCARBON PYROLYSIS 1) RAW MATERIAL Removal of submersibles and replacement of the catapultor. The circuit of the invention is the simplification of the process technology. This goal is achieved by the fact that, in the method of hydrotreatment of liquid products of pyrolysis of hydrocarbon raw materials from unsaturated compounds by heating the raw material in the presence of a polymerization inhibitor - a phenop fraction with a boiling point of 180-270 ° C, separated from the sewage of the semi-coking process. coal, and hydrogen, followed by contacting the mixture with a hydrogenation catalyst, as an inhibitor of polymerization of the phenolic fraction with a boiling point of 18027 ° C, separated from the sewage of the process of semi-coking of coal. The phenol fraction of the sewage process of the semi-coking process of coals contains cresols, xylenols, pyrocatechol, and alkyl pyrocatechins, which effectively prevent side reactions. The method is carried out as follows. Freshly distilled fractions of the liquid pyrolysis products of hydrocarbon feedstocks, such as gasoline, gas oil, dissolved shale and coal, with a boiling point of 30 are inhibited by the phenolic fraction of the sewage of the coal semi-coking process (hereinafter the phenolic fraction). The amount of inhibitor used is O, 001-O, 5% by weight. The inhibited feedstock 35, together with hydrogen, is heated in a heat-sink ennicer to F-ZOO C and sent to the reactor for contact with a catalyst for the hydrogenation of unsaturated compounds. As hydrogenation catalysts, for example, aluminum palladium sulfide, aluminum cobalt molybdenum, aluminum nickel molybdenum are used. The hydrogenation process is carried out in one or several stages. One cubic meter of raw material is supplied with 1OO-1OOO cubic meters of hydrogen. The process pressure is 1 0 -1 0 atm. Volumetric rate O, 5-10.0 volumes of raw material per volume of catalyst per hour. 50 Example 1. The raw material used is a fraction of 35-200 gasoline liquid pyrolysis products (64 0.835, ,, 4760, bromine number - 65.7, diene number - 11.5, the content of actual resins 9, O MG / 1OO ml, the content of aromatic hydrocarbons 75%). The feedstock, together with hydrogenation heating S341 J 10 S, is placed in a tubular heat exchanger and sent to a catalytic hydrogenation reactor. The table shows the effect of the inhibitor used in the proposed method and known on the content of actual resins in the raw material after it is heated in a heat exchanger. OPT is carried out at a pressure of 15 aty, a space velocity of 1 h, the ratio of hydrogen: raw material 2OO. Example 2. Yu, O1 wt.% Inhibitor is added to the feedstock of Example 1 — the phenop fraction, the mixture is heated in a heat exchanger at a pressure of 5 O atm, a space velocity of 3 hours; the ratio of hydrogen; raw materials 2OO and hydrogenate under the same conditions in the presence of aluminum palladium-catalyst. The content of actual resins in the product after heating before the reactor is 15.6 mg / / lOO MP, in the hydrogenation product (reactor loop) 1.2 mg / 100 MP. Example 3. In the feedstock, the fraction with a boiling point of 70 15 ° C is liquid benzyl pyrolysis products (d |, ° -O, 815; I 4-1.518, bromine residue 43.8, the content of actual resins in the freshly distilled fraction is 3.8 mg / OO ml, phenol fraction is added in a quantity of 0.01 wt.%, heated in a heat exchanger at 145 ° C, pressure 40 at, hydrogen: raw materials ratio 200 volumetric velocity for 3 hours. Then hydrogenation is carried out in the presence of an alumina palladium phosphate catalyst in these the same conditions. The content of the actual resin in the raw material after heating 4 D mg / 100 ml, in the hydrogenate 1.0 mg / 1 0O mp. For example, measure 4. In the feedstock, the Cr fraction with a boiling point of 2870 ° C is the liquid pyrolysis products of atmospheric gas oil (d40.7686, n |, 1.4O38, fomnaya number 120, the diene content is 60 wt.%, The content of actual resins in freshly distilled frasdiy3 , 6 mg / 100 ml) Phenopne fraction is added in the amount of O, O2 wt.%, Heated in a heat exchanger at a temperature of 80 ° C, pressure of 40 at. Hydrogen: raw material ratio of 25 O m / m flow rate 3 and hydrogenated in the presence of an aluminum palladium sulfide catalyst in the same conditions Soder can, the actual smop in the product after heating 6.4 mg / 80 ml, in the hydrogenate 1.7 mg / 80 mln. Example 5. In the initial raw material, the fraction with a boiling point of 23 O of the liquid products of pyrolysis of brown coal (Ol 0.96, bromine number 44.5, the content of actual smog in the freshly distilled fraction 12.9 mg / OO ml) is added a phenopic fraction of O, O2 wt.%, Heated in a heat exchanger at a temperature of 1OO C, pressure 40 at, flow rate 1, О, hydrogen: feed 40 O nm / m ratio is hydrogenated under the same conditions in the presence of an aluminum palladium sulfide catalyst. The content of actual resins in giarogenizat 1.5 mg / SC mp. Example 6. (comparative). The process is carried out under the conditions of Example 5, but without the addition of an inhibitor. The used catalyst after the ECO operation loses its activity by 6O%. The heat exchanger is completely clogged with solid polymers. Example 7. In the feedstock a fraction with a boiling point of 25O liquid pyrolysis products a: gas spherical gas oil (bromine number 35.7, actual resin content in the freshly distilled fraction 14, Omg / 10Omp O, 1% by weight of phenol fraction added , heated at a temperature of about 4% at, volumetric rate 1.5: hydrogen: raw materials ratio 200 nm / m and subjected to hydrogenation. The actual content of resins in the hydrogenate is 2.7 mg / 100 ml. The raw materials obtained from the examples of 2-7 may be directed to exhaustive hydrotreating. from unsaturated and sulfur compounds in the presence of oxonic or sulfide hydrotreating catalysts. Example 8. Ionol is added in the raw material of Example 1 in an amount of 0.01 wt.%, heated at a temperature of 85 at, a hydrogen: raw material ratio of 80 °, a space velocity of 6 The amount of deposited coke on the alumina palladium phosphate catalyst is 7.3 wt.%. Using the same raw material with the addition of phenolic fraction in the amount of 0.007 wt.%, the amount of coke on the catalyst is 4.5 wt.% . . When using the method according to the invention, the amount of polymeric products formed is reduced by 2-4 times, the catalyst sponge durability is increased by 10-20%. The method of hydrotreating liquid products of hydrocarbons hydrocarbons from non-areel compounds by heating the raw material in the presence of an inhibitor of polymerisation and hydrogen followed by contacting the mixture with a hydrogenation catalyst, characterized in that, in order to simplify the process of presacess, as a polymerization inhibitor using the fenope fraction with boiling point 1807834108 .8 , vydepeynuyu from wastewater pro-1, USSR Author's Certificate The process of semi-coking coal. Jsfo 216162, CP. C 10 C 1 / OO, 1966. Sources of information, No. 546644, CL. C 10 G 23 / O2, 1974 taken into account in the examination of j (prototype). 2. Copyright testimony of the USSR