SU526281A3 - Method for producing hydrogen-containing gas - Google Patents

Description

The invention relates to the production of a hydrogen-containing gas and to: ukida and gaseous hydrocarbons. The method of hydrogen-containing gas is known by catalytic coking of liquid or gaseous hydrocarbons at a temperature of 550-1000 ° C and a pressure of 1-250 atm in the presence of a nickel-aluminum catalyst. However, with the implementation of such a method, only hydrocarbons containing more than 1 to 10 carbon atoms can be processed, since carbon used as the starting hydrocarbons that are heavier on the catalyst surface and carbon is lost. In addition, the sulfur contained in the original hydrocarbons is a strong home for the nickel-aluminum catalyst, so careful preliminary purification of the hydrocarbons from sulfur is necessary. To prevent soot formation and prolong the service life of the catalyst, it was proposed to use aluminum oxide 1 in mixture with beryllium oxide or calcium, or mixtures, taken in an amount of 10-609:. The addition of oxide to the catalyst of these oxides contributes to the oxide of the resulting carbon converse, thereby eliminating its deposition on the catalyst. The proposed method is applicable to hydrocarbons, the weight of which molecules vary widely - from MCTajia to tons of hydrocarbons, such as kerosene, gas oil, crude oil, etc. In most cases, heavy oil oils contain sulfur in large quantities, but using The proposed catalyst allows them to be processed without prior purification from sulfur, while the catalyst does not lose its activity for a few thousand hours. Oxidized alkali metal oxides prevent thermal polymerization. Aluminum oxide accelerates the interaction of hydrocarbon with steam, and if the catalyst is sintered or crystallized, the aluminum oxide is firmly combined with oxides of alkaline earth metals, with the mechanics of the loose catalysts. In this case, the used aluminum oxide should be of a high degree of shstota, contain silicon dioxide in it, and should be less than 1 wt.%, In I, the prototype should be cjfvi; - ;; on kcht; psopto | This carbon fiber is also found when carbon dioxide in alumin oxide is mixed with impurities of the Perio Group V oxides, the oxidative oxide of the metals AH is more than 10%. oxide g is able to gasify utiodiodorods with a teN / 8frame higher with a high degree of K: o; gsrcS1) .- However, above all, without stress. k; 1lt, ngk sgrotida vertebn kG nrorodhkh lazif ;; kaiit t / lanko nribo its iiekoy t5d; g; era-uru than L | t 1 | L (0) 3c ;; in "; -gk ol.SL ojojci-i ;;. u) r.isi-, Hn- fIpn this (5kost ;.vK-vVifiHbix (Yag words 1 Tr:, л1Л) shchah O; azh K ug: eryl ;; l; 1 kptl} LPy.tor-,; with with ADDED OXYGENOXIDE OXIDE, SOOTYyTs7: B01G and therefore omrc; -;:; 1c o.;:: n :: 1C; YLLO-.CMCJfijKxx: v0.llllol dollars.) (Fr. Jio Kija TiCjj ПГерй 0.ЛЛ;; ;;, Л -:,. Л. (гт -л-; :: ,, l; l; ; l;. ,,;,;: ON 5glg. NS bo.: LL1 |: L: ll;, uch. So; leclio C-iO dozkhkip caa: rapj / "yii 60 les. (.-L ( .n, PLllli-g; l: ..i -: ni: M - W-YO 60 ls.sl, i Tivr; hrrvi f; SL-: (i ion ;; nv; e f-h ;:; 6f :; v V:,.: f-:: -n-4i..i-;::: - iK; i i4 ;; cvt, oxides of Perspire. Crc-sound {C (.; k; and; and , slykuppelno, terg, iskskile ripcDor,: -. Ocri, cat Lilaur ;, contains Oks (, tjkjs jibicoj-air. Wermkksp gg)), silt: wasp oxide and oxide :; l;) ::; OOPS.: xk-al / m-hour C: BeO, b; AlO- - 0 {; -1-: CaH) - 6L2; SrO; -4.32; iVicjO- 5.75. L} Knf. Oraem. Term: 1;, :: cone conductivity oxide lgll ;; v TJ: ;; ra :; llg .g; ironodiuyusti friendl ukszgil-p. X | 1lllg, ill 3; l;, (; l; jMyTij M.ii; ec.a; Fp ;; ak..sh.i tgri nl; l:; ::: -ll-lg lgud h. -: o1-l; 1 ups; lefop ylHIe and LRISUTSTV: LALYA LL: L: 1 ,, ;;, CMCTxUVia s, PNSSHR {M oo / i n :, o,;, s; ..; h, sig ::; l; 1; L:; -: o ;; ; .im arsnl oiejQj gpl.l; and d / 1: Wed;: ch1 / I (I., llsugo about: l :: srp.guru nzgro 1 ---::: -: -; Гч;, гог ::,. р: Л :: /.;:::.г - / ч,.: jiij. l ..;:; y, t;,; u;. ;;, tyl. | za1ipi,.; o / ll:: ld: l L:: About j :: .. About YrlYSHLSSHYUN Yul zrop / l; l; 1l: .L;; s; ls: ll llyut low tsM: b; cpur p ::; chS: P1I. ;; L {;; ,: l. gsh.kpb gomlsrature, ta.G: L; l with:;: L -fo lL; h: l-l ll:;.; l: l {follower4 {; () yullo;

); L1L 1Zhkal

c .; 950 C for lsdogzra; ds1l1: h axis D and. E; 5toktichesky "лл-yutall; olyssl vBJSo fuolze r ;; ; a rk metaldose D ti / rph Dul; taloc; about dsh6; 1 Llyi- {in JiiUorc lpemep. Oksl bsldld11 -; l oddoogal, io toll / s sosozha; D1S q KiT;:,: afI ogyr) LL, d. SL: - dmsg L1chiliu | dosgia; otlol lk; ; corner: e; l, D,; ts oklsk (1.: dllli di; k L1TS otlo Kiix ieMVicpaxypix; link L1.: g; usefulness; l (ok; LL; allaipl k (lllstlo k; glilOg, ll: p -y; :), al; d; ol; -K1L b:, P1 p; 3} S. to;) drsdogzrat the wasp -: dslns;, lforl egs kuitsytsky residual ll / gliya; dada; sat; same as 1S1L ) Llyuztels bsr1; LL11; (it turned out that otlouselle uglsrodl lz lroisholit 60 f 1 I i i i () ii C i i jTo U; i i if n.sfR i g i) i ti ji, nt l -j lOpiis i i i and in П, i i j i п ii u papgs nt j l vioM okksk andrilli. -: l: s |) .ll; l; |; l: id7оь, со; Zll: aglx oxide;, lllll, s, l: lh} 1L1l; n, cx :: KD7ffii i; -iMH ok); sdlo / lil, ios judlls lokomvayut xopotiryio ability, T, OTB)

decomposition or reforming reactions at lower temperatures, and their behavior is the same as the catalysts, which are strontium oxide.

According to the proposed method, steam, air, oxygen or oxygen enriched air are used as the oxidizing agent.

The illustration is illustrated in examples. In Examples 1-9, a tubular reactor (length 1000 mm, internal diameter 50 mm) filled with a catalyst in air (10 mm length, diameter ~ 0 mm), is used.

The tubular reactor is placed in an edektroteesui furnace and heated in it.

The properties of Kuwait’s raw rye oil used in the examples;

Weight, g / cm (d) O.S532

Primary analysis, rev.% 85. (St

C§5-02

il11.50

S2.93

When in the experiments mentioned above, the temperature of the reaction composition is as high as 950 ° C, there is a small oeiii of small carbon with a high content of carbon containing oil from the Kuwaiti cheese.

Example 2. The reforming of the steam in the steam is subjected to a light fraction of oil in the presence of a catalyst of calcium oxide (oxide alio shII).

The conditions created and make the catalysts in the expander mop are as follows:

CE Oilstva frakshi residual oil

Final temperature

boiling C

360 Specific weight, g / cm

0.835

(

Fractional composition, C (American standard test method 1B1):

initial boiling point 33.0

10% 90.5

20% 145.0

30% 189.5

40% 253.0

50% 321.0

60% -357.0

70% 364.0

The volumetric rate in the reactor in examples 1-4 is 2000 hours.

Example, A mixture of StepHJBaw oxide powders and alumina prepared in cooiHoineffliHX zosazann, mixed with water, tricotted and dried at 1300 ° C for several hours, Beo / AljOa catalyst. When these catalysts are used, n-heptane is subjected to reforse in the presence of steam at atmospheric pressure and the results are given in Table. L

Table I

Conditions

Temperature, ° С

Pressure

H, O / C (molar ratio)

Catalyst compositions, 47.350,02,7 37,459,92,7 Calcium oxide content of 10%, preferably 20-60%, effectively prevents carbon deposition. Reforming in the presence of steam residual oils containing even 1-% Zw% sulfur can be carried out without a significant decrease in the activity of the catalysts. It is clear that sulfur compounds of aluminum and calcium, i.e. Alj 83 and CaS are unstable at high temperatures, in particular in the presence of steam, and although a number of oils are converted to hydrogen sulfide, neither CaS nor AB Ss are formed. The study of sulfur in catalysts using x-ray best after their use shows that mainly sulfur atoms in the catalyst are absent. Froze Reforming in the presence of crude steam is carried out using a catalyst containing, in wt.%: A12Oz, 47.3 CaO 50, 0. The following results are obtained: Properties of residual oil (Kuwaiti residual oil fraction) Konesh boiling point, ° C 360 Particular weight, 7835 Elemental content analysis, wt.% Yield based on residual oil% by volume 61.0 React Temperature, S1000 . DavlesheAtmosphere IIj O / C (molar ratio) Volume velocity, hour2,300

Table 2 The composition of the product obtained by the reaction (molar ratio): Hj - 59.5; CO-10, f; C02 - l6,6; CH, -13.4. No carbon deposition is observed. Although a fraction containing 1.26% by weight of sulfur is used as the starting material, the effect of sulfur on the catalyst was not found, there is no change in the catalyst. Example 4 Reforming in the presence of steam is carried out using the same catalyst as in Example 3, however, the pressure is 30 kg / cm. Results. Conditions peaKuj-tH Temperature, ° С Pressure, kg / cm HI О / С (molar ratio) Volume velocity, hour The composition of the product obtained by the reaction (my ratio): Hj - 58.1; CO - 11.3; COj - 13.4; CH4 - 17.2. Deposition of carbon on the catalyst is not possible. Although fractions 1kg containing 2.93% by weight of sulfur are used as raw materials, no effect of sulfur on the catalyst was found, there are no changes in the catalyst; there is no catalyst. EXAMPLE 5 A mixture of beryllium oxide, calcium hydroxide and aluminum hydroxide is mixed with water, briquetted and calcined at 1,300 ° C for several hours to obtain a BeO-CaO-A12Oe catalyst. Using this catalyst, reformed in the presence of steam, n-heptane and Kuwaiti crude oil. The results obtained at atmospheric pressure are shown in Table. 2. The composition of the catalyst, wt.%: BeO - 7.5; CaO- 32.0; AljOs - 59.0. For example, p6. Mixture of beryllium oxide, carbonate | Strontium and alumino hydroxides CMeuJMBawT with water are briquetted and calcined at 1300 ° C for a few hours in order to obtain a BeO-SrO -AljOs catalyst. When using this catalyst refor example. Using a catalyst containing 36.2 wt. SrO, 35.5 wt.% AljO.- ,, 19.5s of CaO and 8.7 weight / A BeO, Kuwaiti residual m is subjected to reforming in the presence of steam under increased pressure.

G1oluch1P1y results

Reaction pressure, kg / cm

thirty

Reaction temperature

W50

4.0

Carbon Steam Ratio

The composition of the gas, mol.%:

ii2

56.3

WITH 12

with,

1.30

2

CIU 18

The reaction lasted 24 hours, but carbon deposition was not observed in the flow of all this time.

In each of the examples, a thermally insulated reactor was used, which has the following dimensions: 1ruby diameter 1.5 m, internal diameter 0.8 m, height 2 m, lined with electrolytic alumina.

Each of the catalysts used in the process according to the present invention may sometimes contain up to 50% by weight of one or more alkaline-earth metal oxides, such as strontium oxide, beryllium oxide, maggot oxide, but the amount of other inorganic impurities is less than J weight .%, in the case of impurities of SiOa and the total amount of oxides of metshov, which are higher than Group V of the Periodic Table, is less than 3 wt.%.

Example Catalysis is subjected to oxidation by crude Kuwaiti oil.

The composition and configuration of the catalyst used, the properties of the supplied oil, the composition of the gas produced, and other components of the reaction (the following reactions follow:

1. The composition of the catalyst, wt.%; A1, O, - 47.3;

CaO - 50.0; other HeoprattHMCCKHe institutions n 7, /.

2. Catalyst configuration: Rage ring-shaped nozzles with an outer diameter of 15 mm, height 15 mm and an outer diameter of 5 mm.

Strength ga.a compression 400 kg / cm in the direction of the axis of the axis of the indra

3. Properties of used oil (Kuwaiti crude oil):

Specific weight, g / cm 0,8532

Prostiidsha Ana; WF, wt.%

C85,08

And 12.50 S2.93

4. Reaction conditions: Temperature, ° С1000 Davlet1e, kg / cm 20

Supply oil, kg / hour 10,000

Par kg / h 5000

Oxygen (959), nm - chas6790

5. Composition of the produced gas, about 5.%: CO - 42.59; CO2 - 5.04; H; - 50.37; N, 0.94; CH - 2.3; Hj S - 0.84.

Claims (3)

The amount of initial reaction materials spent on the production of 100 nm of the output product (From + CO): supplied oil 310, 3kg / 1000nm steam - 155.2 kg /) 000 nm oxygen - 301.0 nm. Sh11gu in the presence of steam iodpergaug n-heptane and | Kuwaiti crude oil at atmospheric (1) oil harlelshI. The results obtained are primed (g century. 3. Composition of the catalyst, wt./g: HCO - 6.4; SrO - 30.8; ACO3 62.5. Table 3: Deposition of carbon on the catalyst was not observed. Even at using oil (oil) containing a large amount of sulfur (2.93 wt.%). The amount of catalyst stretching after 500 hours of sequential use is 360 kg / cm. Example 9. Partial oxidation is carried out using the same type of catalyst and the same oil that were used in example 1, and under stir the air at an appropriate speed to obtain the desired gas composition for use as ammonia synthesis gas. The reaction conditions, the composition of the produced gas are as follows: 1. Reaction conditions: Temperature, ° C Press more, kg / cm Feed oil, kg / hr, kg / h Oxygen (95%), Air, HMV4ac 2. Composition of the produced gas. about 5.%: H- - 38.1; CO - 32.2; SOZ - 5.4; CH4 - HjS - 0.7; N-, 23, 5. 3. The number of initial reaction products spent on the production of 100 nm of effective gas (Hj + CO): supplied oil - 31 1.3 kg / UOPpm; steam - I62,0kg / i000nm oxygen- 236.1nm 1000nm air X -417, Opt / 1000 nm. Deposition of carbon on the catalyst is observed, but there are no changes on the surface of the catzlisato)) but there is no even when using oil containing a large amount of sulfur (2.93 pes.%). Each of the catalysts used in the implementation of the described method has a semi-permanent strength, since these catalysts} {e are such sensitive as a nickel catalyst. The catalysts of the invention are refractory materials. Claims of Invention A method (hydrogen-containing gas by steam or steam-oxygen-oxygen conversion of gaseous or hydrocarbon hydrocarbons with new flared gas) in the presence of a catalyst based on a.chi oxide, characterized in that. that, in order to prevent the formation of soot and prolong the service life of the catcher, alumina-sh1sh oxide is used in a mixture with beryllium oxide, or calcium, or strontium, taken in an amount of 10-60%