CN104549284B - Gaseous hydrocarbon self-heating conversion catalyst and preparation method thereof - Google Patents

Abstract

The invention belongs to gaseous hydrocarbons catalyst technical field, relate to a kind of catalyst for the Autothermal reforming preparing synthetic gas of gaseous hydrocarbon or hydrogen preparation field and preparation method thereof.Catalyst of the present invention is with nickel as active component, with free state SiO₂3Al with mullite structure₂O₃·2SiO₂For carrier, with the oxide of MgO and/or rare earth metal as auxiliary agent.Use beating method or dry pigmentation to prepare semi-finished product, then through molding, roasting, obtain finished catalyst.The anti-carbon performance of this catalyst is strong, has good intensity and strength stability, and active metal dispersion effect is good, and during effectively prevent use, active metal crystal grain is assembled, it is ensured that catalyst activity stability, beneficially large-scale industrial production.

Description

Gaseous hydrocarbon self-heating conversion catalyst and preparation method thereof

Technical field

The invention belongs to gaseous hydrocarbons catalyst technical field, relate to a kind of for the Autothermal reforming preparing synthetic gas of gaseous hydrocarbon Or the catalyst of hydrogen preparation field and preparation method thereof.

Background technology

Along with the minimizing day by day of world petroleum resource, the various gaseous hydrocarbons including refinery gas, natural gas, casing-head gas Development and utilization is increasingly subject to people's attention.Gaseous hydrocarbon contains hydrogen, methane, ethane, propane and fourth according to kind difference Alkane etc..Current industrial application gaseous hydrocarbon hydrogen manufacturing or preparing synthetic gas typically use steam reforming direct translation method.The method is Highly endothermic process, it is desirable to carry out under the conditions of pressure 1.5MPa～3.0MPa, temperature 850 DEG C～900 DEG C, for preventing catalyst from amassing Carbon, needs high steam/hydrocarbons ratio, and energy consumption is high, the H of generation₂It is up to 3 with the mol ratio of CO, is unfavorable for subsequent technique.

The nineties in 20th century, the Autothermal reforming process for preparing synthetic gas of gaseous hydrocarbon becomes study hotspot, and this technique is by portion Dividing a kind of new technology that oxidation and adiabatic steam-reforming combine, methyl hydride combustion is released substantial amounts of heat and is supplied steam reformation, it is achieved anti- Answer device self heat supply, reach adiabatic operation.The party's indirect reformer owned by France method, can be synthesis gas (CO+H by gaseous hydrocarbons₂).Close Become gas the most of many uses, it is possible to for synthetic liquid fuel, methanol, formic acid, methyl ester, dicarbaldehyde etc., to be important change Work raw material.

Compared with tradition steam transforming technique, Autothermal reforming technique has the advantage that

(1) H in product₂/ CO ratio can adjust, can be according to follow-up chemical process needs, by CH in feed change gas₄、 O₂And H₂The ratio of O can prepare multiple different H₂The synthesis gas of/CO.

(2) Autothermal reforming technique is exothermic reaction, carries out, is not required to external heat, reduce fuel in adiabatic reactor Consuming, thermal discharge is little, and energy consumption is low；Reactor volume is little, can reduce floor space；Eliminate heating furnace, device can be greatly decreased Investment.

(3) autothermal reaction is carried out at a higher temperature, and reaction speed is fast, can operate under higher space velocity, and efficiency is high.

At present, the chemical fertilizer industry at home of hydro carbons self-heating Auto-thermal reforming process has been carried out commercial Application, Er Qieying With more successful, but raw materials used it is confined to natural gas.But for a lot of oil plants, to ensure have reliable natural gas to supply Should be the most difficult.In this case, it is considered to the gaseous hydrocarbons such as abundant refinery gas as the unstripped gas of Autothermal reforming technique are The most necessary, but the composition of refinery gas is complex, and often fluctuate.

It is directed to this, in conjunction with the feature of autothermal reaction technique, it is necessary to exploitation one is applicable to that gaseous hydrocarbon is Autothermal reforming urges Agent, to meet autothermal reaction to high activity of catalyst, high intensity and strength stability, good anti-carbon performance and high temperature resistance The particular/special requirement of sintering character.

Chinese patent CN200810046536 discloses a kind of natural gas intermittent conversion town gas catalyst, with kaolinite Soil and aluminium oxide are raw material, and after mechanical ball milling sieves, spin shapes；Under the conditions of 1300 DEG C, 4hr is calcined, i.e. after drying and processing Prepare SiO₂、Al₂O₃Composite oxide carrier, then impregnates active component.Carrier is mainly α-Al mutually₂O₃And Al₆Si₂O₁₃, Account for 80wt%～95wt%；Active component is NiO, accounts for 5wt%～20wt%；Auxiliary agent is selected from Al₂O₃, in rare earth oxide one Plant or multiple.This invention is not directed to Autothermal reforming field.

United States Patent (USP) US4790929 uses Kaolin roasting at 1150～1350 DEG C to be converted into mullite and free dioxy SiClx, is filtered to remove whole or at least some of free silicon dioxide with alkaline aqueous solution, is then dried, the carrier master obtained Mullite to be contained, the most a small amount of free silicon dioxide, the mol ratio of alumina catalyst support/silicon dioxide is 0.50～1.65.Carry One or more in cobalt, nickel, molybdenum, tungsten can be loaded as active component for heavy hydrocarbon removing weight by infusion process on body Metal, or Supported Pt Nanoparticles or palladium are for catalytic cracking of hydrocarbon reaction etc..This invention relates generally to the preparation of carrier, is not directed to self-heating and turns Change field.

Summary of the invention

It is an object of the invention to provide and a kind of be applicable to the Autothermal reforming preparing synthetic gas of gaseous hydrocarbon or the gaseous hydrocarbon of hydrogen preparation field Self-heating conversion catalyst, provides its preparation method being conducive to large-scale industrial production simultaneously.

Gaseous hydrocarbon self-heating conversion catalyst of the present invention, including carrier, active component and auxiliary agent, in described carrier Containing free state SiO₂；

Described catalyst is nickel-silicon-aluminum System Catalyst, and active component is nickel, and carrier is free state SiO₂Do not come The 3Al of stone structure₂O₃·2SiO₂, auxiliary agent be MgO, rare earth element oxide in one or more arbitrary proportion mixing；Respectively The mass fraction of component is:

Nickel content: be calculated as 15～25 parts with NiO；

Carrier: amount to 75～90 parts, wherein 3Al₂O₃·2SiO₂Content is 60～76 parts, and remaining is free state SiO₂, trip Amorph SiO₂Content is 12.5%～16% in the catalyst；

Auxiliary agent: 2～8 parts.

Gaseous hydrocarbon self-heating conversion catalyst preparation method of the present invention, comprises the following steps:

(1) pretreatment of raw material: select containing SiO₂And Al₂O₃Material is raw material, adds NaOH solution mixing, and heating is anti- Should, obtain alkali modification raw material after being filtered, washed and dried；

(2) preparation of catalyst: use beating method or dry pigmentation to prepare catalyst semi-finished product, molding, roasting, obtain finished product Catalyst.

Described containing SiO₂And Al₂O₃Material is that raw material is selected from that Kaolin, bauxite etc. be natural or synthetic mineral The arbitrary proportion mixing of one or more；

Described NaOH solution mass fraction is 10～25%, and addition is as the criterion with whole dipped raw materials needing modification；

Described NaOH solution mass fraction preferably 15～20%, addition is as the criterion with whole dipped raw materials needing modification；

Reacting by heating temperature described in step (1) is 70～100 DEG C, and the response time is 2～6h；

Reacting by heating temperature described in step (1) preferably 80～90 DEG C, the response time is 3～4h；

Beating method step is: by soluble in water to active component predecessor, auxiliary agent precursor solution, add alkali modification raw material, Making beating, dries to obtain semi-finished product；Dry pigmentation step is: by alkali modification raw material, active component predecessor, the mixing of adjuvant component predecessor Rear mechanical ball milling, obtains catalyst semi-finished product.

The mass ratio of the raw material of alkali modification, active component and auxiliary agent is 75～90: 10～25: 2～8；Active component is with NiO Meter, auxiliary agent is in terms of MgO or rare-earth oxide；

Described active component predecessor is one or both arbitrary proportion mixing in nickel nitrate, nickel oxalate；

Described auxiliary agent predecessor is one or more in magnesium nitrate, magnesium oxalate, rare-earth oxalate, rare earth nitrate Arbitrary proportion mixes；

Forming method is for taking 100 parts of semi-finished product, and addition lubricant 3～6 parts, ball milling mixes 15～30min, takes out addition afterwards 5～15 parts of deionized waters, the most compressing；

The lubricant any one or a few arbitrary proportion mixing in graphite, paraffin, stearate；

Forming shape is lamellar or double cellular specially-shaped annular of sphere seven apertures in the human head；Lamellar, particle diameter is 3.5～6mm, and height is 3.5～6mm；Double cellular specially-shaped annulars of sphere seven apertures in the human head, external diameter is 10～16mm, internal diameter 0.5～2.0mm, hole count 7, highly It is 8～11mm；

Sintering temperature is 800～1200 DEG C, and roasting time is 4～9h；

Sintering temperature preferably 900～1150 DEG C, roasting time is 6～8h.

The present invention compared with prior art has the advantages that

(1) its carrier of gaseous hydrocarbon self-heating conversion catalyst described in processes through alkali modification, and adds MgO and/or rare earth Metal-oxide is as auxiliary agent so that carrier meta-alkalescence, thus improves the anti-carbon performance of catalyst；

(2) catalyst processes through high-temperature roasting, and formation mullite, as dominant phase, has good intensity and intensity is steady Qualitative；

(3) make common carrier with porous silicon, increase active metal dispersion, improve catalyst activity surface and use beating method Or dry pigmentation preparation technology both can ensure that catalyst activity, during can avoiding again using, active metal crystal grain is assembled, and protects Card catalyst activity stability, beneficially large-scale industrial production.

Accompanying drawing explanation

Fig. 1 is pressurization activity rating device schematic flow sheet.

In figure: 1, water dosing pump；2, methane, oxygen bottle；3, carburator；4, blender；5, tubular reactor；6, condensation Device；7, separator；8, manostat；9, wet flow indicator.

Detailed description of the invention

Below in conjunction with embodiment, the present invention is described further.

Embodiment 1

Take calcined kaolin (aluminium oxide 35.21%, silicon dioxide 55.31%, impurity≤2%, lower with) add mass fraction 15%NaOH solution keeps 70 DEG C to soak 4h, and filtration washing is to without Na⁺Exist, 120 DEG C of drying, be crushed to 280 mesh.

Weigh nickel nitrate 58.4g, magnesium nitrate 12.8g, be dissolved in 85g water, aqueous solution is joined above-mentioned alkali modification high In the soil 82.5g of ridge, mixing making beating, slurry is put into 120 DEG C of dry 12h in baking oven, obtains semi-finished product A1.

Embodiment 2

Taking calcined kaolin and add 70 DEG C of immersion 4h of mass fraction 15%NaOH solution holding, filtration washing is to without Na⁺Deposit , 120 DEG C of drying, it is crushed to 280 mesh.

Weigh nickel nitrate 66.2g, magnesium nitrate 38.4g, be dissolved in 90g water, aqueous solution is joined above-mentioned alkali modification high In the soil 88g of ridge, mixing making beating, slurry is put into 120 DEG C of dry 12h in baking oven, obtains semi-finished product A2.

Embodiment 3

Taking calcined kaolin and add 75 DEG C of immersion 4h of mass fraction 17%NaOH solution holding, filtration washing is to without Na⁺Deposit , 120 DEG C of drying, it is crushed to 280 mesh.

Weigh nickel nitrate 77.8g, magnesium nitrate 19.2g, be dissolved in 100g water, aqueous solution is joined above-mentioned alkali modification high In the soil 95g of ridge, mixing making beating, slurry is put into 120 DEG C of dry 12h in baking oven, obtains semi-finished product A3.

Embodiment 4

Taking calcined kaolin and add 90 DEG C of immersion 3h of mass fraction 20%NaOH solution holding, filtration washing is to without Na⁺Deposit , 120 DEG C of drying, it is crushed to 280 mesh.

Weigh nickel nitrate 97.3g, magnesium nitrate 25.6g, be dissolved in 100g water, aqueous solution is joined above-mentioned alkali modification high In the soil 98g of ridge, mixing making beating, slurry is put into 120 DEG C of dry 12h in baking oven, obtains semi-finished product A4.

Embodiment 5

Taking calcined kaolin and add 70 DEG C of immersion 4h of mass fraction 20%NaOH solution holding, filtration washing is to without Na⁺Deposit , 120 DEG C of drying, it is crushed to 280 mesh.

Weigh nickel nitrate 89.5g, magnesium nitrate 51.2g, be dissolved in 100g water, aqueous solution is joined above-mentioned alkali modification high In the soil 94.5g of ridge, mixing making beating, slurry is put into 120 DEG C of dry 12h in baking oven, obtains semi-finished product A5.

Implement 6

Taking calcined kaolin and add 80 DEG C of immersion 4h of mass fraction 20%NaOH solution holding, filtration washing is to without Na⁺Deposit , 120 DEG C of drying, it is crushed to 280 mesh.

Weighing nickel nitrate 58g, magnesium nitrate 13g, after drying, mixing is put into ball mill and is milled to 90wt% and crosses 280 mesh sieves, weighs Kaolin 83g and above-mentioned material mixing and ball milling 6h, obtain semi-finished product A6.

Embodiment 7

Taking calcined kaolin and add 70 DEG C of immersion 4h of mass fraction 15%NaOH solution holding, filtration washing is to without Na⁺Deposit , 120 DEG C of drying, it is crushed to 280 mesh.

Weighing nickel nitrate 66g, magnesium nitrate 38g, after drying, mixing is put into ball mill and is milled to 90wt% and crosses 280 mesh sieves, weighs Kaolin 90g and above-mentioned material mixing and ball milling 6h, obtain semi-finished product A7.

Embodiment 8

Taking calcined kaolin and add 75 DEG C of immersion 4h of mass fraction 15%NaOH solution holding, filtration washing is to without Na⁺Deposit , 120 DEG C of drying, it is crushed to 280 mesh.

Weighing nickel nitrate 77.8g, magnesium nitrate 19.5g, after drying, mixing is put into ball mill and is milled to 90wt% and crosses 280 mesh sieves, Weigh Kaolin 98g and above-mentioned material mixing and ball milling 8h, obtain semi-finished product A8.

Embodiment 9

Taking calcined kaolin and add 70 DEG C of immersion 4h of mass fraction 17%NaOH solution holding, filtration washing is to without Na⁺Deposit , 120 DEG C of drying, it is crushed to 280 mesh.

Weighing nickel nitrate 97.3g, magnesium nitrate 25.6g, after drying, mixing is put into ball mill and is milled to 90wt% and crosses 280 mesh sieves, Weigh Kaolin 98g and above-mentioned material mixing and ball milling 7h, obtain semi-finished product A8.

Embodiment 10

Taking calcined kaolin and add 80 DEG C of immersion 3h of mass fraction 20%NaOH solution holding, filtration washing is to without Na⁺Deposit , 120 DEG C of drying, it is crushed to 280 mesh.

Weighing nickel nitrate 89.5g, magnesium nitrate 51.2g, after drying, mixing is put into ball mill and is milled to 90wt% and crosses 280 mesh sieves, Weigh Kaolin 93g and above-mentioned material mixing and ball milling 8h, obtain semi-finished product A10.

Embodiment 11

Semi-finished product prepared by Example 1-10, add graphite by semi-finished product weight 5%, and addition suitable quantity of water is compressing, shape Shape is double cellular specially-shaped annulars of sphere seven apertures in the human head.1100 DEG C of roasting 8h, obtain finished catalyst B1-B10.

Catalyst physical and chemical performance prepared by above-described embodiment 1-11 is as described in Table 1:

Table 1 gaseous hydrocarbon Natural Transformation catalyst physical and chemical performance

For investigating the catalyst performance of the present invention, use the evaluating apparatus shown in Fig. 1 that catalyst is evaluated.

Unstripped gas used by evaluation is casing-head gas after desulfurization, and its component is as shown in table 2.

Table 2 raw material casing-head gas composition (%, v/v)

Evaluating catalyst condition

Process gas is analyzed: Shimadzu GC-8A chromatograph, column length 2m, fills TDX-01, column temperature 45 DEG C, gasifies 100 DEG C, detector 100 DEG C, flow velocity 35mL/min.

Table 3 evaluating catalyst result

In terms of above-mentioned experimental data, the catalyst of preparation has good activity of conversion.The catalyst unloaded after conversion is equal Granule is complete, and color even, without Carbon Deposit Phenomenon, illustrates that catalyst has good anti-carbon nature energy.

For intensity and the strength stability of detection catalyst, measure the sample after the fresh sample of catalyst and heat run respectively Product intensity, has been also carried out detection to the catalyst phosphorus content before and after operating, draws the operating clean coke content of rear catalyst, and result is listed in Table 4.The method of heat run is after 800 DEG C of roasting 3h, to be naturally cooling to room temperature, then survey strong in Muffle furnace by catalyst granules Degree, to detect the strength stability of catalyst.

Table 4 catalyst strength, anti-carbon nature result

Sample number into spectrum	Fresh sample intensity	Intensity after heat run	Strength retention ratio, %	Clean coke content, % after operating
					B1	386	289	77.07	-0.12
B2	375	302	76.26	-0.43
					B3	396	274	78.06	-0.07
B4	351	302	82.51	-0.57
					B5	366	265	69.37	-0.13
B6	382	322	80.70	-0.28
					B7	399	325	93.93	-0.33
B8	346	312	83.20	-0.21
					B9	375	296	77.69	-0.42
B10	381	336	88.19	-0.37

From table 4, it can be seen that catalyst has good intensity and strength stability, can fully meet autothermal process Requirement to catalyst.It addition, the clean coke content after catalyst runs is negative value, further illustrates catalyst of the present invention and have Good coking resistivity.

Comparative example 1

According to implementing 1 scheme, take calcined kaolin (aluminium oxide 35.21%, silicon dioxide 55.31%, impurity≤2%) add The 25%NaOH solution being different from embodiment 1 keeps 70 DEG C to soak 12h, and filtration washing is to without Na⁺Exist, 120 DEG C of drying, pulverize To 280 mesh.

Weigh nickel nitrate 58.4g, magnesium nitrate 12.8g, be dissolved in 85g water, aqueous solution is joined above-mentioned alkali modification high In the soil 82.5g of ridge, mixing making beating, slurry is put into 120 DEG C of dry 12h in baking oven, obtains semi-finished product C1.Treating excess syndrome semi-finished product C1, Adding graphite by semi-finished product weight 5%, addition suitable quantity of water is compressing, is shaped as double cellular specially-shaped annular of sphere seven apertures in the human head.1100 DEG C roasting 8h, obtains finished catalyst D1.

Comparative example 2

By changing concentration and the soak time of NaOH solution in embodiment 1, obtain different content free state SiO₂Urge Agent D2, D3.

Gained catalyst B1 Yu D1, D2, D3, use transmission electron microscope to carry out nickel crystallite relative analysis, and result is listed in table 5；Enter Row activity comparative evaluation, result is listed in table 6.

Table 5 catalyst TEM data contrasts

Table 6 catalyst activity comparative evaluation's data

By table 5 it can be seen that appropriate free state SiO in catalyst₂Existence can improve the dispersion of active metal Ni Degree, and be conducive to improving the agglomeration of active metal.By table 6 it can be seen that contain appropriate free state SiO₂Catalyst Relatively containing a small amount of SiO₂Catalyst, its activity improves a lot.

Claims (7)

1. a gaseous hydrocarbon self-heating conversion catalyst, including carrier, active component and auxiliary agent, it is characterised in that

This catalyst is nickel-silicon-aluminum System Catalyst, and active component is nickel, and carrier is free state SiO₂With mullite structure 3Al₂O₃·2 SiO₂, one or more in MgO, rare earth oxide of auxiliary agent；

The mass fraction of each component is:

Nickel: be calculated as 15～25 parts with NiO；

Carrier: 75～90 parts, wherein 3Al₂O₃·2 SiO₂Content is 60～76 parts, and remaining is free state SiO₂, free state SiO₂Weight/mass percentage composition is 12.5%～16% in the catalyst；

Auxiliary agent: 2～8 parts；

The preparation method of described gaseous hydrocarbon self-heating conversion catalyst, comprises the following steps:

(1) pretreatment of raw material: select containing SiO₂And Al₂O₃Material is raw material, joins NaOH solution soaking, and heating is anti- Should, filter, wash, be dried, ball mill pulverizing obtains alkali modification raw material；

(2) preparation of catalyst: use beating method or dry pigmentation to prepare catalyst semi-finished product, molding, roasting, obtains finished product catalysis Agent.

2. according to the gaseous hydrocarbon self-heating conversion catalyst described in claim 1, it is characterised in that described raw material be Kaolin, The mixture of one or more arbitrary proportions of bauxite.

Gaseous hydrocarbon self-heating conversion catalyst the most according to claim 1, it is characterised in that beating method step is: by activity Component predecessor, auxiliary agent precursor solution are soluble in water, add alkali modification raw material, making beating, dry to obtain semi-finished product；Dry pigmentation step For: by mechanical ball milling after alkali modification raw material, active component predecessor, the mixing of adjuvant component predecessor, obtain catalyst semi-finished product.

Gaseous hydrocarbon self-heating conversion catalyst the most according to claim 1, it is characterised in that forming method is for taking 100 part half Finished product, addition lubricant 3～6 parts, ball milling mixing 15～30 min, rear taking-up adds 5～15 parts of deionized waters, after mixing Compressing.

5. according to the gaseous hydrocarbon self-heating conversion catalyst described in claim 1, it is characterised in that alkali modification raw material, active component Being 75～90: 10～25: 2～8 with auxiliary agent mass ratio, wherein active component is in terms of oxide, and auxiliary agent is in terms of oxide.

6. according to the gaseous hydrocarbon self-heating conversion catalyst described in claim 3, it is characterised in that described active component forerunner Thing is one or both arbitrary proportion mixing in nickel nitrate, nickel oxalate；Described auxiliary agent predecessor be magnesium nitrate, magnesium oxalate, The arbitrary proportion of one or more mixing in rare-earth oxalate, rare earth nitrate.

7. according to the gaseous hydrocarbon self-heating conversion catalyst described in claim 1, it is characterised in that sintering temperature is 800～1200 DEG C, roasting time is 4～9 h.