CN107362806A - A kind of isothermal sulfur-tolerant conversion catalyst and preparation method thereof - Google Patents
A kind of isothermal sulfur-tolerant conversion catalyst and preparation method thereof Download PDFInfo
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- CN107362806A CN107362806A CN201710567427.3A CN201710567427A CN107362806A CN 107362806 A CN107362806 A CN 107362806A CN 201710567427 A CN201710567427 A CN 201710567427A CN 107362806 A CN107362806 A CN 107362806A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The present invention relates to a kind of isothermal sulfur-tolerant conversion catalyst and preparation method, the catalyst is using magnesium aluminate spinel as carrier, active ingredient in catalyst：Cobalt is calculated as the 0.2~20% of catalyst total amount with CoO, and molybdenum is with MoO3The 1~30% of catalyst total amount is calculated as, adds alkali metal composite assistant.Method for preparing catalyst is infusion process.Above-mentioned alkali metal composite assistant plays a part of " alkali metal holder ", and during catalyst use, alkali metal, which is lost in, to be significantly reduced, and improves catalyst low-temperature activity stability.
Description
Technical field
The present invention relates to a kind of isothermal sulfur-tolerant conversion catalyst and preparation method thereof, is lost in more particularly to a kind of alkali metal
Low isothermal sulfur-tolerant conversion catalyst of rate and preparation method thereof.
Background technology
Isothermal sulfur-tolerant conversion process is because of the uniformity of temperature profile in the low and bed with reaction temperature, production control and behaviour
Make it is simpler, flexibly and can effectively avoid methanation side reaction under the conditions of relatively low WGR the advantages that, exist in recent years
It is widely used in New Coal Chemical device.Compared with traditional adiabatic reaction technique, isothermal shift-converter has the following advantages that：
(1) temperature of reactor is low and bed in Temperature Distribution reach unanimity, advantageously in the balance of reaction, therefore being capable of maximum limit
Degree ground plays the performance of catalyst；(2) reaction temperature is adjusted using steam pressure, production is controlled and operated simpler, clever
It is living；(3) under the conditions of relatively low WGR, such as methanation, F-T synthesis and NH3 synthesis may occur for CO transformationreations
Effectively containment is can obtain Deng side reaction or even is prevented.Therefore carry out resistant to sulfur isothermal conversion process and the exploitation of new catalyst has very much
It is necessary.
Resistant to sulfur isothermal conversion process and because reaction temperature is relatively low, WGR is of a relatively high, to the activity of catalyst especially
Low temperature active proposes higher requirement.It is well known that addition alkali metal promoter is that raising catalyst low-temperature activity is maximally effective
Means, but leakage all will inevitably occur in use for alkali metal.And the loss of alkali metal directly affects
The low temperature active and activity stability of catalyst, thus how to reduce alkali metal and be lost in be etc. intermediate temp conversion catalyst development pass
Key.
The content of the invention
The invention provides a kind of alkaline composite assistant, and the alkaline composite assistant is by material A (boehmite, three water aluminium
One or more in stone, aluminium hydroxide, aluminum oxide, aluminium salt), with material B (Mg, K, Na, Ca, Zr, Fe nitrate or sulfuric acid
Salt) by mixing, dry, roasting and smashing are made.The alkaline composite assistant serves the effect of one " alkali metal holder ",
During catalyst use, alkali metal turnover rate substantially reduces, and thereby may be ensured that catalyst low-temperature activity is not suffered a loss.By
The catalyst alkali metal turnover rate of this legal system substantially reduces, and its comparative evaluation's result is as shown in table 1.
A kind of isothermal sulfur-tolerant conversion catalyst, active ingredient in catalyst：Cobalt with CoO be calculated as catalyst total amount 0.2~
20%, molybdenum is with MoO3The 1~30% of catalyst total amount is calculated as, adds alkali metal composite assistant.
The addition of the alkaline composite assistant is the 0.5-50% (percentage by weight) of total catalyst weight；Preferably
0.5-30%.
The catalyst is using any of magnesium aluminate spinel, boehmite, aluminum oxide or several mixtures as load
Body；Such as catalyst carrier is boehmite and magnesium aluminate spinel, both ratios are 1:1-3.
The alkaline composite assistant is K2Al204、Na2Al204、MgAl204、CaAl204、ZrAl204FeAl204、K2SO4、
Na2SO4、CaSO4、ZrSO4、MgSO4In one or more；It is made by above-mentioned alkaline composite assistant preparation method.
The preparation method of the catalyst, comprises the following steps：
The first step：The preparation of alkaline composite assistant
(1) material A and B are mixed；
(2) add suitable quantity of water to be sufficiently mixed, dry, the masterbatch of the obtained alkaline composite assistant of roasting；
(3) alkaline composite assistant masterbatch is carried out crushing obtained alkaline composite assistant.
Wherein, in step (1), material A is one in boehmite, gibbsite, aluminium hydroxide, aluminum oxide, aluminium salt
Kind is a variety of；Material B is Mg, K, Na, Ca, Zr, Fe nitrate or sulfate
Second step：Prepare catalyst
Infusion process：Alkaline composite assistant and carrier material addition peptizing agent are mediated, catalyst is made in extrusion and roasting
Carrier；By containing the described catalyst carrier of active component cobalt and molybdenum mixture co-impregnated solution dipping, then dry or be calcined and be obtained
Catalyst.
Peptizing agent can be nitric acid, or be one kind or more in the nitrate or/and sulfate of alkaline-earth metal, alkali metal
Kind.Peptizing agent dosage is the 0.5-3% weight ratio of carrier.
Pore creating material is additionally added in the preparation process of catalyst, the pore creating material can be sesbania powder, citric acid or methyl-prop
E pioic acid methyl ester.Pore creating material dosage is the 2-10% weight ratio of carrier.
The alkaline composite assistant, in step (2), described drying temperature is 80~200 DEG C, and drying time is 4~12
Hour；Described sintering temperature is 40~650 DEG C, and roasting time is 2~8 hours.
It is 180-300 mesh that alkaline composite assistant, which crushes,.
Embodiment
Clear, complete description will be carried out to the technical scheme in the embodiment of the present invention below.Obviously, described implementation
Example only part of the embodiment of the present invention, rather than whole embodiments.It is common based on the embodiment in the present invention, this area
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
Embodiment 1
200 grams of boehmite is taken, adds KNO350 grams, add 150ml water be well mixed, in 120 DEG C dry and in
Alkaline composite assistant is made in 3 hours in 550 DEG C of roastings, takes 50 grams of boehmite, 100 grams of magnesium aluminate spinel, alkaline composite assistant
20 grams of mixing are uniform, add 10 grams of sesbania powder, mediated with 10% magnesium nitrate solution, and extrusion is simultaneously small in 550 DEG C of roastings 3
When be made carrier.100 grams of carrier is taken, by 12 grams of four molybdenum acid ammonia, 9 grams of cobalt nitrate is made into co-impregnated solution, solution incipient impregnation is carried
Catalyst is made in body, drying and/or roasting.Catalyst numbering is C-1.Its alkali metal turnover rate is as shown in table 1.
Embodiment 2
200 grams of boehmite is taken, adds NaNO380 grams, add 150ml water be well mixed, in 120 DEG C dry and in
Alkaline composite assistant is made in 3 hours in 550 DEG C of roastings, takes 50 grams of boehmite, 100 grams of magnesium aluminate spinel, alkaline composite assistant
20 grams of mixing are uniform, add 10 grams of sesbania powder, mediated with 10% magnesium nitrate solution, and extrusion is simultaneously small in 550 DEG C of roastings 3
When be made carrier.100 grams of carrier is taken, by 12 grams of four molybdenum acid ammonia, 9 grams of cobalt nitrate is made into co-impregnated solution, solution incipient impregnation is carried
Catalyst is made in body, drying and/or roasting.Catalyst numbering is C-2.Its performance comparison is as shown in table 1.
Embodiment 3
200 grams of boehmite is taken, adds KNO350 grams, add 150ml water be well mixed, in 120 DEG C dry and in
Alkaline composite assistant is made in 3 hours in 550 DEG C of roastings, takes 50 grams of boehmite, 100 grams of magnesium aluminate spinel, alkaline composite assistant
30 grams of mixing are uniform, add 10 grams of sesbania powder, mediated with 10% magnesium nitrate solution, and extrusion is simultaneously small in 550 DEG C of roastings 3
When be made carrier.100 grams of carrier is taken, by 12 grams of four molybdenum acid ammonia, 9 grams of cobalt nitrate is made into co-impregnated solution, solution incipient impregnation is carried
Catalyst is made in body, drying and/or roasting.Catalyst numbering is C-3.Its performance comparison is as shown in table 1.
Embodiment 4
200 grams of boehmite is taken, adds K2SO480 grams, add 150ml water be well mixed, in 120 DEG C dry and in
Alkaline composite assistant is made in 3 hours in 550 DEG C of roastings, takes 50 grams of boehmite, 100 grams of magnesium aluminate spinel, alkaline composite assistant
30 grams of mixing are uniform, add 10 grams of sesbania powder, mediated with 10% magnesium nitrate solution, and extrusion is simultaneously small in 550 DEG C of roastings 3
When be made carrier.100 grams of carrier is taken, by 12 grams of four molybdenum acid ammonia, 9 grams of cobalt nitrate is made into co-impregnated solution, solution incipient impregnation is carried
Catalyst is made in body, drying and/or roasting.Catalyst numbering is C-4.Its performance comparison is as shown in table 1.
Embodiment 5
Take 50 grams of boehmite, 100 grams of magnesium aluminate spinel, K2Al20415 grams of mixing are uniform, add sesbania powder 10
Gram, mediated with 10% magnesium nitrate solution, extrusion is simultaneously calcined 3 hours obtained carriers in 550 DEG C.100 grams of carrier is taken, by four
12 grams of molybdenum acid ammonia, 9 grams of cobalt nitrate are made into co-impregnated solution, and by solution incipient impregnation carrier, catalyst is made in drying and/or roasting.
Catalyst numbering is C-5.Its alkali metal turnover rate is as shown in table 1.
Comparative example 1
50 grams of boehmite is taken, 100 grams of mixing of magnesium aluminate spinel are uniform, 10 grams of sesbania powder added, with 10% nitre
Sour magnesium solution is mediated, and extrusion is simultaneously calcined 3 hours obtained carriers in 550 DEG C.100 grams of carrier is taken, by 12 grams of four molybdenum acid ammonia, nitre
Sour 9 grams of cobalt, 16 grams of potassium carbonate are made into co-impregnated solution, and by solution incipient impregnation carrier, catalyst is made in drying and/or roasting.Its
Alkali metal turnover rate is as shown in table 1.
The catalyst potassium lost rate of table 1 contrasts
Catalyst potassium lost rate determines：A certain amount of catalyst sample is weighed, is boiled in boiling water 1 hour, sample is dried
Potassium or sodium content are determined after dry, and compared with sample before boiling, catalyst is represented with the size of potassium or sodium content retention rate
The height of alkali metal turnover rate.
Claims (10)
1. a kind of alkali metal composite assistant, it is characterised in that the alkaline composite assistant, with material B by mixing, is done by material A
Dry, roasting and smashing are made；The material A is one kind in boehmite, gibbsite, aluminium hydroxide, aluminum oxide, aluminium salt
It is or a variety of；The material B is Mg, K, Na, Ca, Zr, Fe nitrate or sulfate.
A kind of 2. isothermal sulfur-tolerant conversion catalyst, it is characterised in that active ingredient in the catalyst：Cobalt is calculated as being catalyzed with CoO
The 0.2~20% of agent total amount, molybdenum is with MoO3The 1~30% of catalyst total amount is calculated as, the alkali metal described in claim 1 is added and answers
Close auxiliary agent.
3. catalyst according to claim 2, it is characterised in that described alkali metal composite assistant is catalyst total amount
0.5~50%.
4. catalyst according to claim 2, it is characterised in that the catalyst with magnesium aluminate spinel, boehmite,
Any of aluminum oxide or several mixtures are carrier material.
5. catalyst according to claim 2, it is characterised in that the alkaline composite assistant is K2Al204、Na2Al204、
MgAl204、CaAl204、ZrAl204、FeAl204、K2SO4、Na2SO4、CaSO4、ZrSO4、MgSO4In one or more.
6. the preparation method of the catalyst described in claim any one of 2-5, it is characterised in that comprise the following steps：
The first step：The preparation of alkaline composite assistant
(1) material A and B are mixed；
(2) add suitable quantity of water to be sufficiently mixed, dry, the masterbatch of the obtained alkaline composite assistant of roasting；
(3) alkaline composite assistant masterbatch is crushed and alkaline composite assistant is made；
Second step：Prepare catalyst
Infusion process：Alkaline composite assistant and carrier material addition peptizing agent are mediated, catalyst carrier is made in extrusion and roasting；
By containing the described catalyst carrier of active component cobalt and molybdenum mixture co-impregnated solution dipping, obtained catalysis is then dried or is calcined
Agent.
7. preparation method according to claim 6, it is characterised in that：The addition of the alkaline composite assistant is 0.5-
30% percentage by weight.
8. preparation method according to claim 6, it is characterised in that peptizing agent is nitric acid or alkaline-earth metal, alkali metal
In one or more nitrate or/and sulfate.
9. preparation method according to claim 6, it is characterised in that in the first step, described drying temperature is 80~200
DEG C, drying time is 4~12 hours；Described sintering temperature is 40~650 DEG C, and roasting time is 2~8 hours.
10. preparation method according to claim 6, it is characterised in that alkaline composite assistant is crushed to 180-300 mesh.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710567427.3A CN107362806B (en) | 2017-07-12 | 2017-07-12 | Isothermal sulfur-tolerant shift catalyst and preparation method thereof |
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| CN201710567427.3A CN107362806B (en) | 2017-07-12 | 2017-07-12 | Isothermal sulfur-tolerant shift catalyst and preparation method thereof |
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| CN107362806A true CN107362806A (en) | 2017-11-21 |
| CN107362806B CN107362806B (en) | 2020-03-10 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111153383A (en) * | 2020-02-27 | 2020-05-15 | 中国华能集团清洁能源技术研究院有限公司 | CO before large-scale combustion2Trapping system |
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| CN103191720A (en) * | 2013-04-26 | 2013-07-10 | 神华集团有限责任公司 | Magnesium aluminate spinel-supported sulphur-tolerant methanation catalyst |
| CN103495421A (en) * | 2013-09-05 | 2014-01-08 | 刘博男 | Sulfur-tolerant methanation catalyst and preparation method thereof |
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2017
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1485416A (en) * | 2002-09-27 | 2004-03-31 | 中国石化集团齐鲁石油化工公司 | Preparation process of immersion for water-gas sulfur-resistant transformation catalyst |
| CN1548228A (en) * | 2003-05-20 | 2004-11-24 | 海 魏 | Sulfur-tolerant CO converting Co-Mo catalyst and its carrier and prepn |
| CN101318137A (en) * | 2008-07-22 | 2008-12-10 | 青岛联信化学有限公司 | High voltage sulphur resistant translation catalyst of CO and preparation method thereof |
| CN101391218A (en) * | 2008-10-31 | 2009-03-25 | 西南化工研究设计院 | Coke-oven gas methanation catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111153383A (en) * | 2020-02-27 | 2020-05-15 | 中国华能集团清洁能源技术研究院有限公司 | CO before large-scale combustion2Trapping system |
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