CN1126598C

CN1126598C - Steam preconversion catalyst for hydrocarbon

Info

Publication number: CN1126598C
Application number: CN99120474A
Authority: CN
Inventors: 郝树仁; 程玉春; 尹长学; 李春禄; 梁卫忠
Original assignee: Qilu Petrochemical Co of Sinopec
Current assignee: China Petrochemical Corp
Priority date: 1999-12-29
Filing date: 1999-12-29
Publication date: 2003-11-05
Anticipated expiration: 2019-12-29
Also published as: CN1301666A

Abstract

The present invention relates to a catalyst for hydrocarbon steam preconversion, which comprises nickel as active metal, alkaline earth metal oxide as an accelerating agent, and a mixture of at least two kinds of inorganic oxide refractories as a carrier, wherein the first kind of inorganic oxide refractory is high porosity inorganic oxide, the second kind of inorganic oxide refractory is high strength inorganic oxide, and the use ratio of the two kinds of inorganic oxide is 1: 0.1 to 0.8. When used for hydrocarbon steam preconversion, the catalyst has strong capacity of adapting to technological conditions, excellent comprehensive performance and high methane yield.

Description

A kind of steam preconversion catalyst for hydrocarbon

The present invention relates to a kind of pre-converting catalyst of hydrocarbon steam conversion, specifically, the present invention relates to a kind of with diatomite/Al ₂O ₃Steam preconversion catalyst for hydrocarbon for carrier.

It is that raw material carries out steam reforming and produces high methane gas under conditions such as low temperature, low steam carbon ratio, high-speed that the hydrocarbon vapours pre-inversion is meant with light oil or lighter hydrocarbons.Produce in the high methane gas process in the hydrocarbon vapours pre-inversion, temperature of reaction generally is controlled at 400～500 ℃, and the employing high activated catalyst, to guarantee that cracking, steam reforming, hydrogenation, reformation and transformationreation can take place higher hydrocarbon at a lower temperature, finally reach methanation and CO shifting balance:

(1) hydrocarbon adsorbs on catalyzer, generates CH in active ingredient and carrier function cracking _X:

C _nH _m→C _n-1H _m-X+CH _X

→C _n-2H _m-2X+CH _X

→C _n-3H _m-3X+CH _X

→……CH _X+CH _X ……………………[1]

(2) CH _XCarry out the water vapor conversion reaction with water vapor and generate H ₂And CO:

(heat absorption) ... [2]

(3) CH _XHydrogenation generates methane:

(heat release) ... [3]

(4) conversion of CO water vapor generates CO ₂And H ₂:

(heat release) ... [4]

(5) methanation reaction of oxycarbide:

(heat release) ... [5]

(heat release) ... [6]

(6) analyse the carbon reaction:

……………………[7]

In above-mentioned reaction, cracking and conversion reaction are thermo-negative reaction, and reactions such as methanation, conversion then are thermopositive reaction, and they can form coupling, mutual heat supplied, thus can reduce and extraneous heat effect.Traditional producing hydrogen from steam conversion is the conversion reaction based on hydrocarbon and steam, it is strong endothermic reaction, need under comparatively high temps, to carry out, and pre-inversion system high methane gas requires cracking, conversion and hydrogenation reaction to carry out simultaneously, the overall thermal effect is less, by the adjusting process parameter, can be implemented in the adiabatic reactor and carry out.

The pre-converting catalyst of using always on the world market has R67GR, R67GR-7H, RKNGR and the RKNGR-7H of Topsoe at present, the 65-2 of ICI, and the G1-80 of BASF, and wherein the R67GR of Topsoe and R67GR-7H are at magnesium-aluminium spinel MgAl ₂O ₄The catalyzer of last nickel-loaded, advantage are the intensity height, and active high, shortcoming is that hydrothermal stability is poor slightly, and the RKNGR of Topsoe and RKNGR-7H are nickel-loaded on MgO, need calcination under higher temperature in the preparation process; The 65-2 of ICI is at Al ₂O ₃Last nickel-loaded; Add a spot of chromium in the G1-8 catalyzer of BASF, to improve activity of such catalysts.

In U.S. Pat 3,429, propose in 680 to make carrier with diatomite, make active constituent with nickel, and do promotor with copper-chromium or copper-chromium-manganese.This catalyzer can further add alkaline earth metal oxide and do promotor, also can add alkaline earth metal oxide.The outstanding advantage of the catalyzer of this invention is to have very high anti-sulphur ability, but its physical strength is poor slightly.

Day the disclosure specially permit among the clear 63-91141 and to propose to use specific surface 350m ²The following silica of/g is made carrier, makes active constituent with nickel, and preparation is used for the catalyzer that methanol steam transforms system methane.Why this invention selects 350m ²The silica carrier that/g is following is that the high temperature active of catalyzer is poor because the contriver thinks that the specific surface of carrier is big, poor heat resistance, and the methane yield is low.The limitation of this catalyzer is it just at the steam reforming of methyl alcohol, and is poor slightly to the hydrocarbon raw material adaptive faculty.

U.S. Pat 4,010 has all proposed the possible general approach of pre-converting catalyst in 008 and US4,160,649, promptly adopts the metal in VIB and the iron family element ting to make catalytic active component, as chromium, molybdenum, tungsten, iron, cobalt, nickel etc.; Adopt the oxide compound of basic metal or alkaline-earth metal to do promotor, as lithium, sodium, potassium, rubidium, beryllium, magnesium, calcium, strontium etc., and these promotor are common and the inorganic oxide refractory support combines, as diatomite, kaolin, aluminum oxide, silicon oxide, boron oxide, hafnia, zirconium white etc. or its mixture.As everybody knows, in the scheme of this general main points, it is impossible or industrial impracticable that many schemes are arranged, as it is just unrealistic to select for use the oxide compound of rubidium to do promotor, because it is the few radioelement of occurring in nature content, the unlikely industrial applicability on a large scale of carrying out; As noted above again catalytic activity component, because the catalytic activity of various metals is different, cost is different, environmental protection toxicity is also different, thereby also can not be the same at the probability of industrial use.With regard to US4,010,008 and US4,160,649, the composition of the catalyzer that is adopted in its technology is: the nickel of 38.0wt% (in metal), diatomite is made carrier, the MgO of 9.0wt% and copper-chromium of 7.5wt%-manganese, wherein copper: chromium: the mol ratio of manganese is 1.0: 1.0: 1.0.

Be lower than under 600 ℃ the condition, catalytic pyrolysis at first takes place in hydro carbons on metal active component (as nickel) surface, and split product is ADSORPTION STATE free radical CH _X, wherein the X value depends on the component of catalyzer, general catalyzer alkalescence strengthens split product CH _XThe X value increase, the speed that generates methane is also fast more, acid strengthen then opposite.Thereby suitably adjust active sites and potential of hydrogen in the catalyzer, it is the important topic in the design of high-performance pre-converting catalyst, and the selection of carrier is also very important, as select for use aluminum oxide to make carrier, then the catalyzer physical strength is better, but because aluminum oxide is comparatively fine and close, the utilising efficiency of catalyzer is low relatively; As select for use diatomite to make carrier, and diatomaceous porosity height, the catalyst utilization height of making, but physical strength is relatively poor relatively.

The pre-converting catalyst that the purpose of this invention is to provide a kind of high comprehensive performance, it not only has excellent mechanical intensity, and has higher methane yield.

In the present invention, the catalytically-active metals component is selected nickel for use, avoids using the bigger chromium of environmental protection toxicity etc., and adopts the promotor of the oxide compound of alkaline-earth metal as catalyzer, and carrier is then selected the blended refractory inorganic oxide for use.The blended refractory inorganic oxide is made up of two classes at least, and wherein the first kind is the inorganic oxide of high porosity, and it provides higher porosity for catalyzer; Second class is high-intensity inorganic oxide, and it provides enough physical strengths for catalyzer.In this blended inorganic oxide refractory support, the ratio of used first kind inorganic oxide and the second used class inorganic oxide is 1: 0.1～1: 0.8, and better proportional range is 1: 0.2～1: 0.6.

In catalyzer of the present invention, used first kind inorganic oxide is at least a kind of in diatomite, kaolin, silicon oxide and the clay, the second used class inorganic oxide is at least a kind of in aluminum oxide and the hydraulicity cement, and hydraulicity cement can be iron cement and/or aluminium cement.

In above-mentioned blended refractory inorganic oxide, preferred assembled scheme is diatomite/aluminum oxide, kaolin/aluminum oxide, silica, silicon oxide/iron cement, silicon oxide/aluminium cement, diatomite/iron cement, diatomite/aluminium cement, kaolin/iron cement and kaolin/aluminium cement; Preferred combination is diatomite/aluminum oxide.

In the above-mentioned catalyzer, the content of first kind inorganic oxide is 10～35wt.%, and better scope is 15～30wt.%; The content of the second class inorganic oxide is 5～25wt.%, and better scope is 5～20wt.%.

In the above-mentioned catalyzer, the content range of active constituent is counted 20～80wt.% with NiO; Better scope is 45～65wt.%.

In the above-mentioned catalyzer, the add-on of alkaline earth metal oxide accounts for 5～30wt.% of total catalyst weight, preferably 10～20wt.%.

The order of selecting for use alkaline-earth oxide to make catalyst promoting agent is the anti-carbon ability that improves catalyzer, improves the basicity of catalyzer simultaneously, to improve the methane yield of pre-converting catalyst.In alkaline-earth oxide, preferably magnesium oxide and/or calcium oxide, more preferably magnesium oxide.

The catalyzer that utilizes mixing inorganic oxide refractory support of the present invention to make has pore structure preferably, not only has small structure, also has a certain amount of macroporous structure, and specific pore volume is greater than 0.20cm ³/ g, the aperture is greater than the pore volume in the hole more than the 25nm, account for more than 5% of porose pore volume, preferably (mercury penetration method mensuration) more than 10%.

The adding mode of alkaline earth metal oxide can be and the carrier blend also to adopt the mode with the co-precipitation of active constituent nickel.Adopt the co-precipitation mode, alkaline-earth oxide can mix better with nickel, is more conducive to the effect performance of basicity in the catalyzer, thereby is more preferred mode.

When preparing above-mentioned catalyzer, can earlier refractory inorganic oxide be mixed, add alkaline earth metal oxide, flood the saline solution of active constituent again; Also refractory inorganic oxide and alkaline earth metal oxide can be mixed together, flood the saline solution of active constituent again; Above-mentioned said mixture can be do to mix, and also can be wet mixing, can also be earlier the saline solution of active constituent saline solution and alkaline earth metal oxide be mixed, and adds alkali and carries out co-precipitation, the dried mixed or wet mixing of co-precipitation and refractory inorganic oxide.Preferably last a kind of co-precipitation/wet mixing mode.

Other step in the catalyst preparation process of the present invention is identical with general Preparation of catalysts step.

According to the catalyzer of the present invention's preparation, physical strength is good, is that the catalyzer radial strength of the die production of Φ 4 can reach more than the 160N/cm with diameter, is that the catalyzer radial strength of the die production of Φ 5 can reach more than the 180N/cm with diameter; And the good combination property of catalyzer of the present invention, the technology adaptive faculty is strong, and the temperature in of pre reformer can change in 300～600 ℃ of scopes, and steam/hydrocarbons ratio can be little to 0.6, high to 5.0 scope, and the liquid air speed of reaction can be from 0.2h ^-1To 8.0h ^-1Simultaneously, utilize the pre-inversion technology methane yield height of catalyzer of the present invention, the yield of methane can reach more than 60% under the general technology condition, and the methane yield can reach more than 70% under the optimized process conditions.。

Accompanying drawing is the catalyst test apparatus of small pressurized, among the figure: the 1-oil-measuring pump; 2-water volume pump; The 3-vaporizer; The 4-mixing tank; The 5-tubular reactor; The 6-condenser; The 7-separator; The 8-potentiostat; The 9-wet flow indicator.

Further specify the present invention below in conjunction with embodiment.

Embodiment 1:

Take by weighing the Ni (NO of industrial one-level respectively ₃) ₂6H ₂Mg (the NO of O 216 grams and industrial one-level ₃) ₂6H ₂O 64 grams are dissolved in 0.5 premium on currency, are mixed with solution; Add industrial one-level sodium carbonate solution to pH greater than 6.5, nickel and magnesium are fully precipitated; Filter, leach thing washing 3 times, oven dry is being higher than 400 ℃ of roastings decomposition; Add 26 gram diatomite (the smart soil of one-level) and 13 gram aluminium stones (industrial one-level), thorough mixing; Add lubricant, play the sheet moulding, make catalyzer C-1, the content of each component and pore structure data see Table-1 among the catalyzer C-1.

Change the add-on of each component in the above-mentioned preparation process, make catalyzer C-2, C-3, C-4 and C-5 respectively, the content of its each component is also listed in table-1 with the pore structure data.

Table-1

Numbering	The content of each component, wt.%				Greater than the shared ratio in the hole of 25nm, %	Specific pore volume (cm ³/g)
	The content of each component, wt.%						NiO	MgO	Diatomite	Al ₂O ₃
	C-1	55	10	25			NiO	MgO	Diatomite	Al ₂O ₃	10	＞18	0.25
C-2	C-1	55	10	25	45	15	25	15	＞20	0.27	10	＞18	0.25
C-2	C-3	25	25	30	45	15	25	15	＞20	0.27	20	＞25	0.42
C-4	C-3	25	25	30	65	10	20	5	＞15	0.22	20	＞25	0.42
C-4	C-5	75	5	15	65	10	20	5	＞15	0.22	5	＞10	0.20

Comparative Examples 1:

With 25 gram iron cement (CaOAl ₂O ₃Fe ₂O ₃, special) and 10 gram kaliophylite (KAlSiO ₄, special) and replace 26 gram diatomite and 13 gram aluminium stones among the embodiment 1, make comparative catalyst B-1;

With 24 gram aluminium cement (CaO2Al ₂O ₃, industrial one-level) and 10 26 gram diatomite and the 13 gram aluminium stones that restrain among the kaliophylites replacement embodiment 1, make comparative catalyst B-2;

Replace the 26 gram diatomite and 13 among the embodiment 1 to restrain the aluminium stones with 38 gram aluminium stones, make comparative catalyst B-3;

With 100ml water glass (Na ₂SiO ₃, SiO ₂Content is 250g/l) and 20 26 gram diatomite and the 13 gram aluminium stones that restrain among the aluminium stones replacement embodiment 1, make comparative catalyst B-4.

Embodiment 2

The evaluating apparatus of steam preconversion catalyst for hydrocarbon is seen accompanying drawing.

It is the pipe of φ 19mm that reaction tubes is selected internal diameter for use, interpolation φ 6mm thermocouples tube.Catalyzer is cut into the small-particle of 10～20 order/inches, filling 60ml.The catalyst reduction medium is a hydrogen, 450 ℃ of reduction temperatures, reduction pressure 0.5MPa, hydrogen air speed 400h ^-1, reduced 6 hours.The prerotation gasification is with gas chromatographic analysis composition and aromaticity content.(1) air speed of Ping Jiaing represents that with petroleum naphtha liquid air speed method of calculation are as follows:

Liquid air speed (LHSV) (h ^-1)=[the naphtha feed amount (ml/min * 60 (min/h)]/catalyst volume (ml) (2) feed water carbon ratio method of calculation are as follows:

H ₂Carbon atom mole number in O/C=water inlet mole number/raw material=

[flooding quantity (ml/min)/18]/[petroleum naphtha amount (ml/min) * density * carbon content (%)/12] (3) oil inlet quantity is calculated as follows formula:

Oil inlet quantity (ml/min)=[LHSV (h ^-1) * catalyst volume (ml)]/60 (min/h) (4) flooding quantity is calculated as follows formula:

Flooding quantity (ml/min)=18/12[H ₂Carbon content (%) in O/C * oil inlet quantity (ml/min) * oil density * oil] (5) methane selectively calculates, and to change into the ratio of methane be methane selectively to carbon in the definition petroleum naphtha, and calculation formula is:

Total carbon (%) (6) transformation efficiency calculates in methane (%) in methane selectively (%)=generation gas/generation gas, and the transformation efficiency of petroleum naphtha refers to that petroleum naphtha is converted into the ratio of carbon one: transformation efficiency (%)=be converted into C ₁The analyzing test data of raw material of oil mass (ml/min)/oil inlet quantity (ml/min) * 100% evaluate catalysts see Table 2, table 3, table 4.

Table 2

Project	Raw material-1 index	Raw material-2 index
Project	Raw material-1 index	Raw material-2 index	Density (kg/m ³)	720.7	737.2
Initial boiling point (℃) 10% 50% 90% final boiling point (℃)	72 87 102 121 151	57 87 121 152 207	Density (kg/m ³)	720.7	737.2
	72 87 102 121 151	57 87 121 152 207	Positive isoparaffin	45.14	64.75
Aromatic hydrocarbons (%)	5.84	11.63	Positive isoparaffin	45.14	64.75
Aromatic hydrocarbons (%)	5.84	11.63	Naphthenic hydrocarbon	49.02	23.62
Main component	C ₅～C ₉	C ₅～C ₁₁	Naphthenic hydrocarbon	49.02	23.62

Catalyzer C-1 is estimated on evaluating apparatus shown in the drawings with above-mentioned raw materials, the results are shown in Table 3.

Table 3

LHSV (h ^-1)	Temperature out (℃)	The prerotation gasification is formed (%)				Selectivity (%)	Transformation efficiency (%)
		The prerotation gasification is formed (%)						CH ₄	CO	CO ₂	H ₂
		4.0	520	66.75	0.5			CH ₄	CO	CO ₂	H ₂	24.7	8.05	72.59	100
5.0	521	4.0	520	66.75	0.5	66.45	0.57	24.8	8.18	72.37	100	24.7	8.05	72.59	100
5.0	521	6.0	518	66.25	0.6	66.45	0.57	24.8	8.18	72.37	100	24.8	8.35	72.29	100
7.0	520	6.0	518	66.25	0.6	65.75	0.6	24.7	8.95	72.21	100	24.8	8.35	72.29	100
7.0	520	8.0	520	65.8	0.6	65.75	0.6	24.7	8.95	72.21	100	24.9	8.7	72.07	91

Appreciation condition: pressure 4.0MPa, steam/hydrocarbons ratio 1.5,450 ℃ of temperature ins, 260 hours comparative examples 2 of evaluation time

B-1, B-2, B-3 and B-4 estimate during with the raw material identical with embodiment 2, method and evaluating apparatus comparative catalyst, and evaluation result sees Table 4, table 5, table 6 and table 7.

Table 4

LHSV (h ^-1)	Temperature in (℃)	Temperature out (℃)	The prerotation gasification is formed (%)				Selectivity (%)	Transformation efficiency (%)
			The prerotation gasification is formed (%)						CH ₄	CO	CO ₂	H ₂
			1.0	415	480	59.4			CH ₄	CO	CO ₂	H ₂	0.43	24.9	15.27	70.1	100
1.0	415	480	1.0	415	480	59.4	48.6	0.8	24.2	26.4	66.0	100	0.43	24.9	15.27	70.1	100
1.0	415	480	0.7	421	480	52.4	48.6	0.8	24.2	26.4	66.0	100	0.53	24.5	22.57	67.7	100
1.0	420	480	0.7	421	480	52.4	55.2	0.48	24.3	20.02	69.0	78	0.53	24.5	22.57	67.7	100

Appreciation condition: pressure 3.0MPa, steam/hydrocarbons ratio 2.0, evaluation time 36 hours

Table 5

LHSV (h ^-1)	Temperature in (℃)	Temperature out (℃)	The prerotation gasification is formed (%)				Selectivity (%)	Transformation efficiency (%)
			The prerotation gasification is formed (%)						CH ₄	CO	CO ₂	H ₂
			1.0	423	482	59.3			CH ₄	CO	CO ₂	H ₂	0.43	24.7	15.6	70.2	100
0.7	430	480	1.0	423	482	59.3	58.8	0.38	24.5	16.3	70.3	100	0.43	24.7	15.6	70.2	100
0.7	430	480	1.0	443	500	57.9	58.8	0.38	24.5	16.3	70.3	100	0.59	24.5	17.0	69.8	100
1.0	480	520	1.0	443	500	57.9	56.2	0.80	24.5	17.8	68.1	100	0.59	24.5	17.0	69.8	100
1.0	480	520	1.5	480	520	52.9	56.2	0.80	24.5	17.8	68.1	100	0.72	24.0	22.4	68.2	86

Appreciation condition: pressure 3.0MPa, steam/hydrocarbons ratio 2.0, evaluation time 100 hours

Table 6

LHSV (h ^-1)	Temperature in (℃)	Temperature out (℃)	The prerotation gasification is formed (%)				Selectivity (%)	Transformation efficiency (%)
			The prerotation gasification is formed (%)						CH ₄	CO	CO ₂	H ₂
			1.0	425	485	58.8			CH ₄	CO	CO ₂	H ₂	0.39	23.3	17.51	71.3	100
1.0	430	485	1.0	425	485	58.8	55.0	0.39	23.2	21.41	70.0	100	0.39	23.3	17.51	71.3	100
1.0	430	485	1.0	450	510	50.3	55.0	0.39	23.2	21.41	70.0	100	0.60	22.7	26.4	68.3	83

Appreciation condition: pressure 3.0MPa, steam/hydrocarbons ratio 2.0, evaluation time 24 hours

From table 4 to table 6 evaluation result as can be seen, B-1, B-2, the catalyzer of B-3 system is used for the light oil pre-inversion all can not reach the ideal effect.

Table 7

LHSV (h ^-1)	Temperature out, ℃	Pressure, MPa	H ₂O /C	The prerotation gasification is formed (%)				Selectivity, %	Transformation efficiency, %
				The prerotation gasification is formed (%)						CH ₄	CO	CO ₂	H ₂
				1.0	478	2.0	2.0			CH ₄	CO	CO ₂	H ₂	60.4	0.49	23.8	15.31	71.3	100
1.0	519	2.0	2.0	1.0	478	2.0	2.0	54.6	0.90	23.4	21.1	69.2	100	60.4	0.49	23.8	15.31	71.3	100
1.0	519	2.0	2.0	1.0	520	2.0	1.5	54.6	0.90	23.4	21.1	69.2	100	58.2	1.10	23.5	17.2	70.3	100
1.0	520	4.0	1.5	1.0	520	2.0	1.5	62.1	0.74	23.6	13.6	71.8	100	58.2	1.10	23.5	17.2	70.3	100
1.0	520	4.0	1.5	2.0	520	4.0	1.5	62.1	0.74	23.6	13.6	71.8	100	63.1	0.78	23.7	12.4	72.0	100
3.0	515	4.0	1.5	2.0	520	4.0	1.5	63.1	0.76	23.8	12.3	72.0	100	63.1	0.78	23.7	12.4	72.0	100
3.0	515	4.0	1.5	4.0	521	4.0	1.5	63.1	0.76	23.8	12.3	72.0	100	62.4	0.83	23.9	12.9	71.6	100
5.0	520	4.0	1.5	4.0	521	4.0	1.5	63.8	0.78	24.4	11.0	71.7	88	62.4	0.83	23.9	12.9	71.6	100

Appreciation condition: 450 ℃ of temperature ins

Find out that from table 7 and table 3 result it is respond well that Ni-MgO/ silicon-the aluminium System Catalyst is carried out pre-inversion, and be best with Ni-MgO/ diatomite-alumina sample.

Embodiment 3

Under processing condition such as different steam/hydrocarbons ratios, temperature of reaction, reaction pressure and air speed, the pre-inversion performance of C-1 catalyzer is investigated, the result lists in table 8 respectively to table 11.

(1) steam/hydrocarbons ratio is to catalyzer C-1 pre-inversion Effect on Performance

Table 8

Sequence number	H ₂O/C	The prerotation gasification is formed (%)				Transformation efficiency (%)	Selectivity (%)
		The prerotation gasification is formed (%)						CH ₄	CO	CO ₂	H ₂
		1	3.0	55.7	0.86			CH ₄	CO	CO ₂	H ₂	25.4	18.04	100	67.96
2	2.0	1	3.0	55.7	0.86	61.4	0.95	25.3	12.34	100	70.04	25.4	18.04	100	67.96
2	2.0	3	1.5	65.5	0.96	61.4	0.95	25.3	12.34	100	70.04	25.4	8.14	100	71.36
4	1.0	3	1.5	65.5	0.96	70.3	1.12	25.4	3.18	100	72.61	25.4	8.14	100	71.36
4	1.0	5	0.8	71.5	1.39	70.3	1.12	25.4	3.18	100	72.61	24.3	2.81	100	73.57
6	0.6	5	0.8	71.5	1.39	72.8	2.0	23.8	1.37	100	73.81	24.3	2.81	100	73.57
6	0.6	7	0.4	74.3	2.02	72.8	2.0	23.8	1.37	100	73.81	23.0	0.7	Oil penetrates	74.82

Appreciation condition: the stationary liquid air speed is 4.0h ^-1, pressure is 4.0MPa, temperature of reaction is 450 ℃, exports 520 ℃; Steam/hydrocarbons ratio is 0.8 o'clock, enters the mouth 430 ℃, and steam/hydrocarbons ratio drops at 0.6 o'clock, 420 ℃ of inlet controls

Can find out that from table 8 evaluation result along with the decline of steam/hydrocarbons ratio, methanation reaction is accelerated, purpose product methane content constantly raises in the pre-inversion product, the corresponding rising of selectivity; Because the branch drops of water, the CO shifting balance is moved to the left, and CO content raises; The hydrocarbon steam conversion reaction reduces relatively, and hydrogen content constantly descends.

The minimum steam/hydrocarbons ratio of light oil thermodynamics under 4.0MPa, 420 ℃ of conditions is 0.55, steam/hydrocarbons ratio is to enter thermodynamics carbon distribution district at 0.4 o'clock, carbon trend at first appears analysing in raw material in the ingress, cracking catalyst, conversion and hydrogenation activity descend, and under the high-speed effect, unreacted raw material constantly down penetrates, it is more and more violent to analyse the carbon reaction, cause whole bed catalyst carbon distribution, resistance increases fast, the catalyzer rapid deactivation.

At steam/hydrocarbons ratio is under 0.6 condition, pre-inversion reaction can be carried out more smoothly, illustrate that the C-1 catalyzer has good cracking, conversion and hydrogenation activity, and three reactions are coordinated mutually, guarantee the rapid cracked of heavy hydrocarbon simultaneously, guaranteed the carrying out of hydrocarbon steam conversion reaction again, the hydrogen of generation in time makes the further dehydrogenation of cracking intermediate product analyse carbon for the split product hydrogenation provides necessary hydrogen source just to be unlikely.

(2) temperature of reaction is to catalyzer C-1 pre-inversion Effect on Performance

Table 9

Sequence number	Bed temperature, ℃				The prerotation gasification is formed, %				Transformation efficiency %	Selectivity %
	Bed temperature, ℃				The prerotation gasification is formed, %						Inlet	1/3	2/3	Outlet	CH ₄	CO	CO ₂	H ₂
	1	400	415	451	450	70.2	0.27	24.6			Inlet	1/3	2/3	Outlet	CH ₄	CO	CO ₂	H ₂	4.93	100	73.87
2	1	400	415	451	450	70.2	0.27	24.6	411	440	483	489	68.3	0.44	24.9	6.36	100	72.94	4.93	100	73.87
2	3	412	460	506	520	65.9	0.95	25.4	411	440	483	489	68.3	0.44	24.9	6.36	100	72.94	7.96	100	71.38
4	3	412	460	506	520	65.9	0.95	25.4	450	460	481	477	69.7	0.41	24.6	5.29	100	73.87	7.96	100	71.38
4	5	450	480	500	495	66.3	0.65	24.9	450	460	481	477	69.7	0.41	24.6	5.29	100	73.87	8.15	100	72.94
6	5	450	480	500	495	66.3	0.65	24.9	450	497	519	518	61.6	0.81	24.9	10.69	100	71.38	8.15	100	72.94
6	7	500	520	548	550	59.9	1.43	23.5	450	497	519	518	61.6	0.81	24.9	10.69	100	71.38	15.17	100	70.61
8	7	500	520	548	550	59.9	1.43	23.5	500	520	582	600	52.7	2.8	22.2	22.3	100	67.82	15.17	100	70.61

Appreciation condition: steam/hydrocarbons ratio 1.5, liquid air speed is 4.0h ^-1, pressure is 4.0MPa.

Table 9 result can find out that the hydrocarbon steam conversion reaction that the rising of temperature helps absorbing heat takes place, and the hydrogen of generation and carbon monoxide increase, and are unfavorable for that the methanation reaction of heat release carries out, and methane content descends in the reaction product, and methane selectively descends.

(3) system pressure is to catalyzer C-1 pre-inversion Effect on Performance

Table 10

Sequence number	Pressure (MPa)	The prerotation gasification is formed (%)				Selectivity (%)	Transformation efficiency (%)
		The prerotation gasification is formed (%)						CH ₄	CO	CO ₂	H ₂
		1	0.5	50.3	2.4			CH ₄	CO	CO ₂	H ₂	25.1	22.2	64.65	100
2	1.0	1	0.5	50.3	2.4	55.95	1.74	25.25	17.06	67.46	100	25.1	22.2	64.65	100
2	1.0	3	2.0	60.95	1.28	55.95	1.74	25.25	17.06	67.46	100	25.55	12.32	69.51	100
4	3.0	3	2.0	60.95	1.28	64.3	0.94	25.65	9.11	70.74	100	25.55	12.32	69.51	100
4	3.0	5	4.0	65.5	0.89	64.3	0.94	25.65	9.11	70.74	100	25.4	8.21	71.36	100

Appreciation condition: 450 ℃ of bed temperature ins, 520 ℃ of temperature outs, steam/hydrocarbons ratio 1.5, liquid air speed is 4.0h ^-1

Whole reaction system is the reaction that volume increases, and the reduction reaction pressure helps reaction and carries out.Yet to the purpose product, under transformation efficiency 100% situation, improve reaction pressure, have significant effect generating methane.Because the pressurize methanation reaction increases, hydrogen content descends in the reactant gases; The CO transformationreation is to generating CO ₂Direction moves, and CO content descends.Methane content improves, CO content reduces all is that pre-inversion reaction is desired, carries out to the product direction of purpose so the pressure rising helps pre-inversion.

(4) air speed is to catalyzer C-1 pre-inversion Effect on Performance

Table 11

Sequence number	LHSV (h ^-1)	The prerotation gasification is formed (%)				Selectivity (%)	Transformation efficiency (%)
		The prerotation gasification is formed (%)						CH ₄	CO	CO ₂	H ₂
		1	4.O	66.75	0.5			CH ₄	CO	CO ₂	H ₂	24.7	8.05	72.59	100
2	5.O	1	4.O	66.75	0.5	66.45	0.57	24.8	8.18	72.37	100	24.7	8.05	72.59	100
2	5.O	3	6.0	66.25	0.6	66.45	0.57	24.8	8.18	72.37	100	24.8	8.35	72.29	100
4	7.0	3	6.0	66.25	0.6	65.75	O.6	24.7	8.95	72.21	100	24.8	8.35	72.29	100
4	7.0	5	8.0	65.8	0.6	65.75	O.6	24.7	8.95	72.21	100	24.9	8.7	72.07	91

Appreciation condition: steam/hydrocarbons ratio 1.5, pressure 4.0MPa, 450 ℃ of temperature ins, 520 ℃ of temperature outs.

As can be seen from Table 11, the variation of air speed is little to the influence of pre-inversion reaction product.Mention 8.0h ^-1The time begin to have a small amount of light oil to penetrate.

Embodiment 4

Carry out low temperature and the test of high steam/hydrocarbons ratio pre-inversion with catalyzer C-2 of the present invention, and carry out hydrogen-oil ratio adjustment test.The results are shown in Table 12.Testing raw materials used is Ying Shan chemical plant hydrogen feedstock, and promptly raw material 2.Bed ten location points of average mark from top to bottom marks the reaction hotspot location.

Table 12

Condition	Hydrogen-oil ratio	Steam/hydrocarbons ratio	Bed temperature, ℃			Gas production rate 1/min	Conversion tail gas is formed, %			Selectivity %	Transformation efficiency %	Hotspot location
			Bed temperature, ℃			Gas production rate 1/min	Conversion tail gas is formed, %			Selectivity %	Transformation efficiency %	Hotspot location	Inlet	In 1	Outlet		CH ₄	CO	CO ₂
			Temperature	100 100 100 100	1.5 1.5 1.5 1.5	450 450 450 450	509 491 478 470	481 463 440 437	4.4 4.25 4.28 4.25	65.3 67.4 69.7 69.7	0.49 0.39 0.31 0.28	22.8 22.9 23.1 23.1	Inlet	In 1	Outlet		CH ₄	CO	CO ₂				100 100 100 100	73.7 74.3 74.9 74.9	4 4 4 4
Temperature	100 200 200 200 200 200 70 70	3.5 3.5 3.5 3.5 3.5 3.6	Temperature	100 100 100 100	1.5 1.5 1.5 1.5	450 450 450 450	509 491 478 470	481 463 440 437	4.4 4.25 4.28 4.25	65.3 67.4 69.7 69.7	0.49 0.39 0.31 0.28	22.8 22.9 23.1 23.1	450 425 400 385 370 360	483 463 449 438 428 410	479 455 439 424 416 410	4.86 4.8 4.64 4.65 4.58 4.46	56.5 61.2 64.2 66.2 68.3 68.6	0.34 0.22 0.18 0.14 0.13 0.12	23.7 22.5 22.6 22.7 22.7 22.8	70.2 72.9 73.8 74.5 75.0 75.0	100 100 100 100 100 100	3 4 4 5 5 6	100 100 100 100	73.7 74.3 74.9 74.9	4 4 4 4
		3.5 3.5 3.5 3.5 3.5 3.6	1.5 1.5	361 351	440 432	417 420	4.31 4.25	72.6 72.1	0.19 0.24	23.8 23.7	75.2 75.1	100 100	450 425 400 385 370 360	483 463 449 438 428 410	479 455 439 424 416 410	4.86 4.8 4.64 4.65 4.58 4.46	56.5 61.2 64.2 66.2 68.3 68.6	0.34 0.22 0.18 0.14 0.13 0.12	23.7 22.5 22.6 22.7 22.7 22.8	70.2 72.9 73.8 74.5 75.0 75.0	100 100 100 100 100 100	3 4 4 5 5 6	7 8
		Steam/hydrocarbons ratio	1.5 1.5	361 351	440 432	417 420	4.31 4.25	72.6 72.1	0.19 0.24	23.8 23.7	75.2 75.1	100 100	70 70 70	3.5 2.5 1.5	360 360 361	372 390 440	410 417 417	4.36 4.38 4.31	66.1 68.5 72.6	0.12 0.16 0.19	24.3 23.8 23.8	72.9 74.1 75.2	7 8	100 100 100	9 9 8
Hydrogen-oil ratio	200 100 70	Steam/hydrocarbons ratio	3.5 3.5 35.5	360 360 360	410 392 372	410 409 410	4.46 4.43 4.36	68.6 67.4 66.1	0.12 0.11 0.12	22.8 23.6 24.3	75.0 74.0 72.9	100 100 100	70 70 70	3.5 2.5 1.5	360 360 361	372 390 440	410 417 417	4.36 4.38 4.31	66.1 68.5 72.6	0.12 0.16 0.19	24.3 23.8 23.8	72.9 74.1 75.2	6 7 8	100 100 100	9 9 8

Appreciation condition: hydrogen to oil volume ratio is 100, pressure 3.0MPa, liquid air speed 3.0h ^-1, catalyst loading 60ml, granularity 10～20 order/inches, bed height 260mm.

Claims

1. catalyzer that is used for the hydrocarbon vapours pre-inversion, reactive metal is a nickel in the catalyzer, and the oxide compound of employing alkaline-earth metal is as the promotor of catalyzer, the carrier that it is characterized in that catalyzer adopts two class refractory inorganic oxides at least, the first kind is the inorganic oxide of high voidage, be at least a kind of in diatomite, kaolin, silicon oxide and the clay, second class is high-intensity inorganic oxide, be at least a kind of in aluminum oxide and the hydraulicity cement, the usage ratio of two class inorganic oxides is 1: 0.1 to 1: 0.8.

2. the described catalyzer of claim 1, the ratio that it is characterized in that the inorganic oxide of used first kind high voidage and the used high-intensity inorganic oxide of second class be 1: 0.2 to 0.6.

3. the described catalyzer of claim 1 is characterized in that used hydraulicity cement is at least a kind of in iron cement and the aluminium cement.

4. the described catalyzer of claim 1, the inorganic oxide that it is characterized in that used first kind high voidage is a diatomite, the used high-intensity inorganic oxide of second class is an aluminum oxide.

5. the described catalyzer of claim 1 is characterized in that first kind inorganic oxide content is 10wt.% to 35wt.% in the catalyzer, and the second class inorganic oxide content is 5wt.% to 25wt.%

6. the described catalyzer of claim 5 is characterized in that first kind inorganic oxide content is 15wt.% to 30wt.% in the catalyzer, and the second class inorganic oxide content is 5wt.% to 20wt.%.

7. the described catalyzer of claim 1, the content that it is characterized in that NiO in the catalyzer is 20wt.% to 80wt.%.

8. the described catalyzer of claim 7, the content that it is characterized in that NiO in the catalyzer is 45wt.% to 65wt.%.

9. the described catalyzer of claim 1, the content that it is characterized in that alkaline earth metal oxide in the catalyzer is 5wt.% to 30wt.%.

10. the described catalyzer of claim 9, the content that it is characterized in that alkaline earth metal oxide in the catalyzer is 10wt.% to 20wt.%.

11. claim 1,9 or 10 described catalyzer is characterized in that alkaline earth metal oxide contained in the catalyzer is magnesium oxide and/or calcium oxide.

12. the described catalyzer of claim 11 is characterized in that alkaline earth metal oxide contained in the catalyzer is a magnesium oxide.

13. the described catalyzer of claim 1, it is characterized in that aperture in the catalyzer greater than the pore volume in 25nm hole account for more than 5% of porose pore volume.

14. the described catalyzer of claim 1, it is characterized in that aperture in the catalyzer greater than the pore volume in 25nm hole account for more than 10% of porose pore volume.