CN1385361A - Large pore structured hydrocarbon steam convertion catalyst - Google Patents

Large pore structured hydrocarbon steam convertion catalyst Download PDF

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CN1385361A
CN1385361A CN 01108414 CN01108414A CN1385361A CN 1385361 A CN1385361 A CN 1385361A CN 01108414 CN01108414 CN 01108414 CN 01108414 A CN01108414 A CN 01108414A CN 1385361 A CN1385361 A CN 1385361A
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catalyst
carrier
oxide
cao
hydrocarbon steam
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CN1192974C (en
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蒋毅
郑林
程极源
李孝维
王华明
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CHUANHUA GROUP CO LTD
Chengdu Institute of Organic Chemistry of CAS
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CHUANHUA GROUP CO LTD
Chengdu Institute of Organic Chemistry of CAS
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Abstract

The present invention provides a catalyst for preparing synthetic gas by means of hydrocarbon steam conversion. It uses alpha-Al2O3 and CaCO3 as raw material, through the processes of mixing, forming and roasting, and obtains the CaO-Al2O3 compound oxide carrier, then adopts separated impregnation or co-impregnation method to impregnate the carrier with active component (nickel oxide), anti-carbon adjuvant (rare earth oxide) and accelerant (transition metal oxide), and makes it undergo the process of roasting so as to obtain the invneted catalyst. Said catalyst possesses macroporous structure distribution, its pore colume is greater than or equal to 0.2 ml/g, and the pores whose pore size is greater than or equal to 300 mm are above 60% of total pore volume of said catalyst.

Description

A kind of hydrocarbon steam conversion catalyst of macroporous structure
The present invention relates to hydrocarbon steam conversion preparing synthetic gas (hydrogen and carbon monoxide) and use catalyzer.
In synthetic ammonia and synthesizing methanol industry, be that the producer of raw material generally adopts the steam reforming preparing synthetic gas with Sweet natural gas (or oil field gas), and the converter of synthetic gas special use and process cost account for more than 60% of whole cost.Adopt low steam carbon ratio to transform and can save process steam, reduce the reburner gas consumption, the cost that is conducive to enterprise product descends.AMV process water carbon ratio as Britain ICI company is 2.75, and the steam/hydrocarbons ratio of LCA technology is 2.5, and the energy-saving ammonia factory steam/hydrocarbons ratio of Denmark TOPS φ e company exploitation is generally all 2.5～3.0, and energy-saving effect is fairly obvious, but adopts noble metal catalyst more, and price is higher.
State's inner catalyst is with α-Al mostly 2O 3Be the Ni catalyst of carrier, the raw water carbon ratio that is used for Large Scale Synthetic Ammonia Plants is 3.2～3.8.If will reduce the steam/hydrocarbons ratio of converter, the problem that may occur is: along the catalyzer of conversion tube inlet section (0～2m, 450～550 ℃ of sections), be subjected to the long duration of action of low-temperature oxidation atmosphere 1., the easy passivation of ortho states Ni of going back that with the aluminum oxide is carrier generates NiO, and the catalyzer activity of conversion is descended; 2. be subjected to the outer influence of conducting heat of pipe of high heat flow rate per unit area, the easy carbon deposit of the catalyzer of conversion tube top (2～5m, 550～675 ℃ of sections) is pulverized, and causes bed resistance to increase and stops.
In order to address the above problem, Chinese scholars has been carried out big quantity research.At first be the activity of conversion of catalyzer, particularly low temperature active, the method for employing is that the profile of catalyzer is produced different shape to increase geometrical surface by original Raschig ring.As the wheel shape C11-9-09 catalyzer of U.S. UCI company, the Denmark honeycombed R67-7H of TOPS φ e company catalyzer, with groove Raschig ring RG5C catalyzer of French APC company etc.The conversion catalyst trade mark of numerous domestic is also copied on geometric shape, as the Z111/CN16 type (honeycombed) of southwestern chemical research institute, and the Z112-1Q/2Q type (porous spherical) of river company limited by shares catalyst plant etc.The effective ways that improve the anti-carbon deposit performance of catalyzer normally add various anti-charcoal auxiliary agents, as basic metal, alkaline-earth metal, rare earth oxide, precious metal or transition metal oxide etc., as CN1182715, CN1154944, CN1131638, CN85102194, CN1157256 etc.
The novel conversion catalyst that the purpose of this invention is to provide a kind of macroporous structure, can not only show good low temperature active, the catalyst breakage that can effectively reduce carbon deposit simultaneously and avoid causing because of the duct obstruction, thereby can make the long-time running under the condition of steam/hydrocarbons ratio 2.5～3.0 of this catalyzer, to satisfy of the requirement of energy-saving synthetic ammonia new technology to conversion catalyst.
The object of the present invention is achieved like this:
With α-Al 2O 3, CaCO 3Be raw material, its proportioning α-Al 2O 3: CaCO 3=1: 0.05～0.40 (weight ratio), after adding an amount of expanding agent and lubricant, through mixing, moulding is sintered into CaO-Al under 1300 ℃～1450 ℃ 2O 3Composite oxide carrier (A).The phase of carrier is α-Al 2O 3And CaAl 2O 4, CaAl wherein 2O 4Content should be greater than 5% of vehicle weight.This carrier pore volume 〉=0.25ml/g, in the pore size distribution, the macropore of 〉=300nm accounts for more than 80% of the total pore volume of carrier.
Flood active component (NiO) and anti-charcoal auxiliary agent rare earth oxide (RE with the method that branch soaks or soaks altogether in carrier A xO y) and promoter transition metal oxide (M xO y), dipping namely makes macroporous catalyst by 450 ℃～650 ℃ roastings.Wherein rare earth oxide can be the single rare earth oxide compound, also can be mixed rare-earth oxide, and transition metal oxide is one or more of Mn, Cr, Co, Cu oxide compound.Catalyzer is by weight percentage formed:
NiO 8～20％
RE xO y 0.5～3％
M xO y 0.3～2％
All the other are carrier.
The catalyst expression that makes take the branch method of soaking is as NiO-M xO y/ RE xO y/ CaO-Al 2O 3, the catalyst expression that makes take the method for soaking altogether is as NiO-M xO y-RE xO y/ CaO-Al 2O 3Wherein, RE xO yRare earth oxide, M xO yIt is transition metal oxide.
Expanding agent is one or more of carbonate, nitrate, powdered carbon, cellulose family, starch or macromolecular compound; Lubricant is that stearate, graphite are or/and paraffin.
CaO-Al 2O 3The moulding of composite oxide carrier can with pressure ring or mould injection forming technology, be made high geometric outer surface long-pending porous spherical or porous column shape.
Soak method or the catalyzer that makes of the method for soaking altogether with branch, after all can in 500 ℃～800 ℃ following nitrogen atmosphere, being reduced into Ni-M/RE/A and Ni-M-RE/A catalyzer, being applicable under the condition of raw water carbon ratio 2.5～3.0, is the technological process of the steam reforming preparing synthetic gas of raw material with the Sweet natural gas.
The present invention has following advantage:
1. aspect catalyst carrier, by to α-Al 2O 3The modification of carrier, the CaO-Al that makes 2O 3Composite oxide carrier, its pore volume is big, and the macropore prosperity is conducive to the catalyst based anti-Coking Behavior of Ni and the improvement of antioxygenic property.
2. aspect the preparation technology of catalyst, the order that carrier soaks or soaks altogether with branch is added rare-earth oxide and transition metal oxide in Ni is catalyst based, be conducive to improve the decentralization of nickel, thereby improves active and anti-Coking Behavior.
3. in the catalyst pores configuration aspects, because the pore volume of carrier is big, the macropore prosperity, make in the pore size distribution of catalyzer, the macropore of aperture 〉=300nm accounts for more than 60% of the total pore volume of catalyzer, thereby improves activity of such catalysts utilization rate of inner surface, the enforcement that helps saving energy and reduce the cost.
Proved with contrast experiment's data below.
Experiment adopts the mobile gradientless reactor of thermosyphon circulation to measure catalyzer low temperature (650 ℃) activity of conversion of industrial granularity, and (%) represents with methane conversion.Condition determination is P=1.0Mpa, H 2O/CH 4=2.0 (moles), methane flow rate: 50 mark liters/hour.Reductive condition: H 2-N 2(～30%H 2), 650 ℃ of reductase 12s hour.The coke content of catalyzer after running in 16 hours adopts temperature programming oxygen burning-chromatography (TPO) to measure (wt%).
For the ease of with α-Al 2O 3For the Ni catalyst of carrier compares, reforming catalyst with the domestic application success, Z111/CN-16 (sample-1), Z112-1Q/2Q (sample-2), and soak legal system standby sample-3 by the present invention with branch, be expressed as follows with the chemical composition (percetage by weight) of soaking altogether legal system standby sample-4:
Sample-1:20.47NiO-2.16La 2O 3/ α-A1 2O 3
Sample-2:17.32NiO-2.92Y 2O 3/ α-Al 2O 3
Sample-3:15.44NiO-0.68CuO/1.95La 2O 3/ CaO-Al 2O 3
Sample-4:16.74NiO-2.21 (La 2O 3-Y 2O 3)-1.82MnO 2/ CaO-Al 2O 3
Its performance comparison the results are shown in Table 1 and table 2.
The pore structure data of table 1 catalyzer
The activity of conversion of table 2 catalyzer and coke content
Figure A0110841400072
Above result shows that the prepared catalyzer of the present invention has good activity of conversion, demonstrates unique anti-carbon deposit performance simultaneously, is applicable to the technological process of energy-saving Sweet natural gas (or oil field gas) steam reforming preparing synthetic gas.
Below be embodiments of the invention.
Embodiment one
Take by weighing 165.0 gram α-Al 2O 3, 13.2 grammes per square metre matter calcium carbonate, after in porcelain dish, mixing, 22 milliliters of the methylcellulose of adding 1%, calcium stearate 6.6 grams, graphite 1.2 grams mix pressure ring moulding (φ 16mm, Raschig ring), under 1350 ℃ ± 10 ℃ conditions, calcined 6 hours again, namely make CaO-Al 2O 3Composite oxide carrier A.
The pore volume that records carrier A is 0.25ml/g, side pressure strength 310 newton/centimetre.
Get 5 in above-mentioned carrier (about 10 grams), be the nickel nitrate solution of 220 grams per liters with concentration, concentration is the yttrium nitrate solution of 280 grams per liters, concentration is the mixed liquor dipping of the lanthanum nitrate hexahydrate of 240 grams per liters, dipping is 0.5 hour under 85 ℃ temperature, is filtered dry, in air atmosphere, roasting is 0.5 hour under 500 ℃ of conditions, makes 11.42NiO-1.81 (La 2O 3-Y 2O 3)/CaO-Al 2O 3Catalyst.Embodiment two
Take by weighing 165.0 gram α-Al 2O 3, 62.6 gram precipitated calcium carbonates, concentration is 27 milliliters of 1.3% methylcellulose, carbon dust 1.8 grams mix, pressure ring moulding (φ 16mm, Raschig ring), again calcining 4 hours under 1430 ℃ ± 10 ℃ conditions namely makes CaO-Al 2O 3Composite oxide carrier A.
The pore volume that records carrier A is 0.31ml/g, side pressure strength 230 newton/centimetre.
Get 5 in above-mentioned carrier (about 10 gram), use immersion condition repeated impregnations, the roasting twice identical with embodiment one, namely make 19.42NiO-2.93 (La 2O 3-Y 2O 3)/CaO-Al 2O 3Catalyst.
Embodiment three
Take by weighing 165.0 gram α-Al 2O 3, 33.0 restrain precipitated calcium carbonates, carbon dust 3.8 grams, and the paraffin 25ml that adds again thermosol mixes, and mould injection forming (φ 13mm, 3 hole spheries) gives earlier dewaxing under 200 ℃～300 ℃, calcines 5 hours under 1380 ℃ ± 10 ℃ conditions again, namely makes CaO-Al 2O 3Composite oxide carrier A.
The pore volume that records carrier A is 0.26ml/g, side pressure strength 330 newton/centimetre.
Get 5 in above-mentioned carrier (about 10 gram), immersing concentration under 80 ℃～85 ℃ conditions is in the nickel nitrate solution of 220 grams per liters, takes out after 0.5 hour to be filtered dry, and again roasting 1 hour under 550 ℃ of conditions namely makes and contains 9.7NiO/CaO-Al 2O 3Catalyst.Repeated impregnations under similarity condition then, roasting once makes 17.1NiO/CaO-Al 2O 3Catalyst.
The pore volume that records this catalyzer is 0.21ml/g, side pressure strength 335 newton/centimetre.
Embodiment four
Get the three made CaO-Al by embodiment 2O 35 of composite oxide carriers (about 10 grams) are the lanthanum nitrate hexahydrate of 52.5 grams per liters with concentration, under 80 ℃～85 ℃ conditions, flood to take out after 0.5 hour and are filtered dry, and again roasting 1 hour under 550 ℃ of conditions must contain 3.54La 2O 3The semi-finished product of/A impregnated in semi-finished product in the copper nitrate mixed solution of nickel nitrate that concentration is 220 grams per liters and 38.5 grams per liters, through being filtered dry again, roasting under 550 ℃ of conditions, repeated impregnations under similarity condition then, roasting once namely makes 15.44NiO-0.68CuO/1.95La 2O 3/ CaO-Al 2O 3Catalyst.
The pore volume that records this catalyzer is 0.23ml/g, side pressure strength 350 newton/centimetre.Embodiment five
Get the three made CaO-Al by embodiment 2O 35 of composite oxide carriers (about 10 grams) are the nickel nitrate of 220 grams per liters with concentration, the lanthanum nitrate of 26.25 grams per liters, after 30.15 the manganese nitrate solution of the yttrium nitrate of grams per liter and 41.5 grams per liters mixes, carrier A be impregnated in this mixed solution, be filtered dry, roasting.Immersion condition gets 16.74NiO-2.21 (La with embodiment three 2O 3-Y 2O 3)-1.82MnO 2/ CaO-Al 2O 3Catalyst.
The pore volume that records this catalyzer is 0.25ml/g, side pressure strength 320 newton/centimetre.
Embodiment six
Get the three made CaO-Al by embodiment 2O 3Composite oxide carrier A (5, about 10 gram) is the nickel nitrate of 180 grams per liters with concentration, after the cobalt nitrate solution mixing of the yttrium nitrate of 30.15 grams per liters and 18.5 grams per liters, carrier A be impregnated in this mixed solution flood, and is filtered dry roasting.Immersion condition is with embodiment three, makes to contain 12.83NiO-0.81Y 2O 3-0.77CoO/CaO-Al 2O 3Catalyst.
The pore volume that records this catalyzer is 0.23ml/g, side pressure strength 330 newton/centimetre.
The activity of conversion of gained catalyzer and anti-carbon deposit performance.
The foregoing description three, four, five, six prepared catalyst samples (φ 13mm, 3 hole balls, single) are respectively charged into the gradientless reactor of industrial granularity, activity of conversion and the coke content after 16 hours under measuring 650 ℃.Condition determination the results are shown in Table three as previously mentioned.
The activity of conversion of table three catalyzer and coke content
Table three data show: by the present invention preparation with CaO-Al 2O 3Composite oxides are the Ni-based reforming catalyst of carrier, owing to contain anti-charcoal auxiliary agent (rare earth oxide) and promoter (transition metal oxide), catalyst is macroporous structure and distributes, and is conducive to the raising of activity of conversion and the improvement of anti-Coking Behavior.

Claims (8)

1 one kinds of hydrocarbon steam conversion catalyst for preparing synthetic gas are made up of carrier, active component, auxiliary agent, it is characterized in that, carrier is CaO-Al 2O 3Composite oxides, the phase of carrier are α-Al 2O 3And CaAl 2O 4
2 by the described hydrocarbon steam conversion catalyst for preparing synthetic gas of claim 1, it is characterized in that carrier is with α-Al 2O 3, CaCO 3Be raw material, by weight ratio α-Al 2O 3: CaCO 3=1: 0.05～0.40, add an amount of expanding agent and lubricant, through mixing, moulding is sintered into CaO-Al at 1300 ℃～1450 ℃ 2O 3Composite oxide carrier.
3 by the described hydrocarbon steam conversion catalyst for preparing synthetic gas of claim 2, it is characterized in that expanding agent is one or more of carbonate, nitrate, carbon dust, cellulose family, starch or macromolecular compound; Lubricant is that stearate, graphite are or/and paraffin.
4 by the described hydrocarbon steam conversion catalyst for preparing synthetic gas of claim 2, it is characterized in that CaO-Al 2O 3The moulding of composite oxide carrier can with pressure ring or mould injection forming technology, be made high geometric outer surface long-pending porous spherical or porous column shape.
5 by claim 1 or 2 described hydrocarbon steam conversion catalyst for preparing synthetic gas, it is characterized in that, the catalyst activity component is NiO, auxiliary agent is rare earth oxide and transition metal oxide, rare earth oxide can be the single rare earth oxide compound, also can be mixed rare-earth oxide, transition metal oxide is one or more of Mn, Cr, Co, Cu oxide compound, and catalyzer by weight percentage consists of:
NiO 8～20％
Rare earth oxide 0.5～3%
Transition metal oxide 0.3～2%
All the other are carrier.
6 by the described hydrocarbon steam conversion catalyst for preparing synthetic gas of claim 5, it is characterized in that, the catalyst expression that makes take the branch method of soaking is as NiO-M xO y/ RE xO y/ CaO-Al 2O 3, wherein, RE xO yRare earth oxide, M xO yIt is transition metal oxide.
7 by the described hydrocarbon steam conversion catalyst for preparing synthetic gas of claim 5, it is characterized in that, the catalyst expression that makes take the method for soaking altogether is as NiO-M xO y-RE xO y/ CaO-Al 2O 3, wherein, RE xO yRare earth oxide, M xO yIt is transition metal oxide.
The application of the described catalyzer of 8 claims 5 in the technological process that with Sweet natural gas or oil field gas is feedstock production ammonia or methyl methanol syngas.
CN 01108414 2001-05-11 2001-05-11 Large pore structured hydrocarbon steam convertion catalyst Expired - Fee Related CN1192974C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102319574A (en) * 2011-05-17 2012-01-18 太原理工大学 Synthesis gas methanation catalyst and preparation thereof
CN104258867A (en) * 2014-08-22 2015-01-07 萍乡庞泰实业有限公司 A catalyst for natural gas steam reforming and a preparing method thereof
CN105032432A (en) * 2014-12-12 2015-11-11 北京恩泽福莱科技有限公司 Catalyst used for preparing bio-based n-alkanes and preparation method thereof
CN110898826A (en) * 2018-09-18 2020-03-24 中国石油天然气股份有限公司 Pr-containing alumina carrier and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101108350B (en) * 2006-07-18 2010-05-12 中国石油天然气股份有限公司 Hydrocarbon steam conversion catalyst and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102319574A (en) * 2011-05-17 2012-01-18 太原理工大学 Synthesis gas methanation catalyst and preparation thereof
CN104258867A (en) * 2014-08-22 2015-01-07 萍乡庞泰实业有限公司 A catalyst for natural gas steam reforming and a preparing method thereof
CN104258867B (en) * 2014-08-22 2016-06-29 江西庞泰环保股份有限公司 Natural gas steam reforming catalyst and preparation method thereof
CN105032432A (en) * 2014-12-12 2015-11-11 北京恩泽福莱科技有限公司 Catalyst used for preparing bio-based n-alkanes and preparation method thereof
CN105032432B (en) * 2014-12-12 2017-11-14 北京恩泽福莱科技有限公司 Catalyst for preparing bio-based n-alkane and preparation method thereof
CN110898826A (en) * 2018-09-18 2020-03-24 中国石油天然气股份有限公司 Pr-containing alumina carrier and preparation method thereof

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