CN107774288A - Be carbonized Si modification sulfur-resistant transformation catalyst and preparation method thereof - Google Patents
Be carbonized Si modification sulfur-resistant transformation catalyst and preparation method thereof Download PDFInfo
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- CN107774288A CN107774288A CN201610749557.4A CN201610749557A CN107774288A CN 107774288 A CN107774288 A CN 107774288A CN 201610749557 A CN201610749557 A CN 201610749557A CN 107774288 A CN107774288 A CN 107774288A
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
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Abstract
The invention belongs to sulfur-resistant transformation catalyst technical field, and in particular to one kind carbonization Si modification sulfur-resistant transformation catalyst and preparation method thereof.Described catalyst, include the chemical composition of following mass ratio：Al2O322.0~45.0%；MgO 7.0~15%；MoO36.5~10.0%；CoO 1.5~5.0%；SiO225.0~45.0%；TiO21.0~6.0%；Surplus is C.Catalyst of the present invention has good structure and activity stability, service life length, suitable for harsh conditions such as high temperature, high pressure, high-speeds, the preparation method, simple possible, is readily produced.
Description
Technical field
The invention belongs to sulfur-resistant transformation catalyst technical field, and in particular to one kind carbonization Si modification sulfur-resistant transformation catalyst
And preparation method thereof.
Background technology
Maximization, the scale requirement of current coal gasification development, and the CO of high content is converted in coal gasifying process gas, it is right
Sulfur-resistant transformation catalyst proposes new demand：(1) when transformationreation occurs for the process gas of high CO contents, reaction heat significantly increases
Add, it is desirable to which catalyst has good resistance to elevated temperatures；(2) large-minded due to handling, loaded catalyst is necessarily significantly increased,
Also more conventional design load is high for gas air speed, it is desirable to which sulfur-resistant transformation catalyst will not only have higher intensity and flushing resistance, also
There should be higher shift activity of resistance to high-speed etc..Importantly, Sinopec intends newly-built coal chemical engineering equipment, gasification process
CO contents reach as high as more than 70% in gas, and the process gas of the quality enters transformation system, and exothermic heat of reaction amount dramatically increases, bed
Temperature increases, and the harmful effects such as transformation catalyst overtemperature sintering, active rapid decrease is easily caused, to the high temperature resistant of catalyst
Performance proposes higher requirement.But industrial sulfur-resistant transformation catalyst resistance to elevated temperatures is poor at present, during higher than 500 DEG C, urge
Agent activity stability is remarkably decreased, the lost of life.In the case, the conversion catalysis of novel fire resistant high concentration CO is developed
Agent turns into field key technical problem urgently to be resolved hurrily.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide one kind carbonization Si modification sulfur-resistant transformation catalyst, tool
There are good structure and activity stability, the high temperature that is particularly suitable for use in, high pressure, high-speed conversion harsh conditions, extending catalyst makes
Use the life-span；Present invention simultaneously provides its preparation method.
Carbonization Si modification sulfur-resistant transformation catalyst of the present invention, include the chemical composition of following mass ratio：
The preparation method of described carbonization Si modification sulfur-resistant transformation catalyst, comprises the following steps：
(1) first, aluminum contained compound, magnesium-containing compound and titanium-containing compound are well mixed, then, addition carborundum,
After silica and active carbon powder mix, ball mill ball milling is put into 1~2 hour, add binding agent and be well mixed to obtain mixture；
(2) it is ammonium molybdate is soluble in water, it is added in the mixture that step (1) obtains, mediates；
(3) it is cobalt nitrate and magnesium nitrate is soluble in water, it is added in the mixture after the kneading that step (2) obtains, again
Mediate；
(4) the mixture extrusion forming after the kneading again for obtaining step (3), dries, roasting, obtains finished catalyst.
Wherein：
In step (1), described aluminum contained compound, magnesium-containing compound and titanium-containing compound are powdered.
In step (1), described aluminum contained compound is boehmite, aluminum oxide or aluminium glue, preferably boehmite.
In step (1), described magnesium-containing compound is magnesia, magnesium oxalate, magnesium carbonate or magnesium stearate, is preferably aoxidized
Magnesium, more preferably light magnesium oxide.
In step (1), described titanium-containing compound is metatitanic acid or titanium oxide, preferably metatitanic acid.
In step (1), described carborundum is porous silicon carbide, is not less than 150m than surface2/g。
Carborundum is mostly prepared by high temperature sintering, more relatively low than surface, and discomfort is fit to do this catalyst carrier, and the present invention uses city
The porous silicon carbide sold, carborundum more more conventional than surface are big.
In step (1), described activated carbon is wood activated charcoal, is not less than 300m than surface2/g。
In roasting process, activated carbon can partly form porous silicon carbide silicon structure with silica, partly be closed with magnalium titanizing
Thing forms composite spinelle structure, improves the intensity and thermal structure stability of catalyst.In addition it is also basis that activated carbon, which is selected,
Catalyst determines to the demand of pore structure in itself, mainly considers the suction-operated to hydrogen sulfide.
In step (1), described binding agent is two or more in starch, sucrose, sesbania powder, citric acid or oxalic acid
Mixture.Two or three preferably in starch, sucrose, sesbania powder, citric acid or oxalic acid, more preferably citric acid and sesbania
Powder.
The dosage of described binding agent is respectively aluminum contained compound, magnesium-containing compound, titanium-containing compound, carborundum, oxidation
The 2~4% of gross mass after silicon and active carbon powder roasting.Gross mass after described roasting is according to this several material in roasting temperature
Loss on ignition under degree is obtained by theoretical calculation.For example, when binding agent is citric acid and sesbania powder, the dosage of citric acid be containing
The 2~4% of gross mass after aluminium compound, magnesium-containing compound, titanium-containing compound, carborundum, silica and active carbon powder roasting,
The dosage of sesbania powder is also aluminum contained compound, magnesium-containing compound, titanium-containing compound, carborundum, silica and active carbon powder roast
The 2~4% of gross mass after burning.
In step (2), described kneading time is 2~10 minutes.
In step (3), described kneading time again is 5~15 minutes.
In step (4), described drying is natural drying.
In step (4), described sintering temperature is 500~800 DEG C, and the time is 2~6h.
In summary, beneficial effects of the present invention are as follows：
(1) resistant to sulfur pre-transform catalyst of the present invention forms magnesia-alumina spinel structure, carborundum and magnalium in roasting process
The composite spinelle structure of titanium composition, using the magnesia-alumina spinel structure of formation, composite spinelle structure and carborundum as carrier,
During pyroreaction, heat caused by transformationreation in catalyst duct can in time be removed well, prevent sintering of catalyst from leading
Cause hydraulic performance decline.The high chemical stability of carborundum also makes it not have a negative impact to original catalyst active center.This
Outside, carborundum also has good hydrogen sulfide adsorption performance in itself, is advantageous to the vulcanization of active constituent oxide, to a certain extent
Improve catalyst activity.
(2) while carborundum is added, further optimize catalyst preparation process, adjust active component and auxiliary agent plus
Enter mode and distributional pattern, fortifying catalytic agent structure and activity stability, so as to which fortifying catalytic agent is in high temperature, high pressure, high-speed
Etc. structure and activity stability under harsh conditions, extend its service life, there is economic and social benefit well.
(3) preparation method, simple possible, is readily produced.
Embodiment
With reference to embodiment, the present invention will be further described.
All raw materials used in embodiment are purchased in market unless otherwise specified.
Embodiment 1
44.0g aluminium glues, 50.0g magnesium stearates, 5.0g titanium dioxide powders are well mixed, addition 18.5g carborundum,
35.0g silica and 12.0g active fruit shell carbon powder are well mixed, and are put into ball mill ball milling 2.0 hours, then each addition 2.0g fields
Cyanines powder and 3.0g starch, which are well mixed, forms mixture A, and 12.4g ammonium molybdates are dissolved in 20mL deionized waters, adds above-mentioned mixed
In compound A, mediate 10 minutes；16.0g cobalt nitrates and 13.0g magnesium nitrates are dissolved in 25mL deionized waters, continuously add mixing
In thing A, mediate 10 minutes, extrude and be in strip, spontaneously dry, be calcined 2h at 800 DEG C, produce finished catalyst.
Embodiment 2
45.0g aluminum oxide, 37g magnesium oxalates, 2.5g metatitanic acid powder are well mixed, add 10g carborundum, 10g oxidations
Silicon and 2g active fruit shell carbon powder are well mixed, and are put into ball mill ball milling 1 hour, then each addition 3g sesbania powders and the mixing of 3g sucrose
Mixture A is formed uniformly, 10.0g ammonium molybdates are dissolved in 15mL deionized waters, is added in said mixture A, is mediated 8 minutes；
16g cobalt nitrates and 18.5g magnesium nitrates are dissolved in 30mL deionized waters, continuously added in mixture A, mediates 15 minutes, extrudes
It is in strip, spontaneously dries, is calcined 2h at 650 DEG C, produces finished catalyst.
Embodiment 3
30.0g boehmites, 8.0g light magnesium oxides, 7.5g metatitanic acid powder are well mixed, add 9.5g carbonizations
Silicon, 20.0g silica and the coconut activated carbon powders of 4g are well mixed, and are put into ball mill ball milling 1.5 hours, then each addition 4g lemons
Acid and 3g starch, which are well mixed, forms mixture A, and 11.0g ammonium molybdates are dissolved in 20mL deionized waters, add said mixture A
In, mediate 2 minutes；6g cobalt nitrates and 7.4g magnesium nitrates are dissolved in 15mL deionized waters, continuously added in mixture A, is mediated
10 minutes, extrude and be in strip, spontaneously dry, be calcined 4h at 700 DEG C, produce finished catalyst.
Embodiment 4
57.0g boehmites, 20g magnesium carbonate, 1.3g metatitanic acid powder are well mixed, addition 18.3g carborundum,
7.5g silica and 1.5g active fruit shell carbon powder are well mixed, and are put into ball mill ball milling 2 hours, then it is each add 2g sesbania powders and
4g oxalic acid is well mixed to form mixture A, and 8.0g ammonium molybdates are dissolved in 15mL deionized waters, adds in said mixture A, pinches
Close 10 minutes；20.0g cobalt nitrates and 14.8g magnesium nitrates are dissolved in 35mL deionized waters, continuously added in mixture A, is mediated
15 minutes, cloverleaf pattern is extruded into, is spontaneously dried, 6h is calcined at 500 DEG C, produces finished catalyst.
Embodiment 5
40.0g boehmites, 6.0g light magnesium oxides, 3.0g titanium dioxide powders are well mixed, add 10.7g carbonizations
Silicon, 25.0g silica and 5.0g active fruit shell carbon powder are well mixed, and are put into ball mill ball milling 2 hours, then each addition 3g sesbanias
Powder and 3g citric acids, which are well mixed, forms mixture A, and 11.7g ammonium molybdates are dissolved in 20mL deionized waters, add above-mentioned mixing
In thing A, mediate 5 minutes；14.0g cobalt nitrates and 14.8g magnesium nitrates are dissolved in 25mL deionized waters, continuously add mixture A
In, mediate 15 minutes, extrude and be in strip, spontaneously dry, be calcined 3h at 800 DEG C, produce finished catalyst.
Pressurization activity rating device in known technology is used to simulate industrial condition, and measure " former granularity " catalyst is in difference
Under the conditions of tail gas carbonomonoxide concentration and its change, compare the performances such as shift activity and the stability of catalyst, overall merit is urged
The properties of agent.Reaction tube is 45 × 5mm of Ф stainless steel tube, and there is 8 × 2mm of Ф thermocouples tube in center.According to different water
Gas than requirement be incorporated a certain amount of water, after high-temperature gasification, reaction tube is entered together with unstripped gas, and to carry out Water gas shift/WGS anti-
Should, tail gas chromatograph after reaction.
Unstripped gas forms：CO contents：50.0% (V/V)；CO2Content：3.0% (V/V)；H2S contents：＞ 0.2%；Surplus：
H2；
Loaded catalyst：50mL；
Catalyst vulcanization condition：Temperature：250℃；Pressure：2.0MPa；Dry gas air speed：2000h-1；Water/gas：1.0；H2S contains
Amount：0.3%；Time：20h；
Sulfur-resistant transformation catalyst pressurization appreciation condition：
Inlet temperature：450℃；Pressure：4.0MPa；Water/gas：1.20；Dry gas air speed：3000h-1；H2S contents：0.2%~
0.4%；Time：40h.
Respectively prepared by commercially available industrial catalyst, embodiment 1-5 using the pressurization activity rating device in known technology
Finished catalyst carries out catalyst activity and just evaluated, then successively according to sulfur-resistant transformation catalyst pressurization harsh conditions one, two institute
Row condition carries out harsh conditions aging to catalyst respectively, after aging, carries out catalyst activity evaluation again, contrasts harsh conditions
Activity change situation after aging, concrete outcome are shown in Table 1.
The catalytically active assessment result of the embodiment 1-5 finished catalysts of table 1
Sulfur-resistant transformation catalyst pressurization harsh conditions one：
Inlet temperature：500℃；Pressure：4.0MPa；Water/gas：1.20；Dry gas air speed：4000h-1；H2S contents：0.3%；
Time：100h.
Sulfur-resistant transformation catalyst pressurization harsh conditions two：
Inlet temperature：450℃；Pressure：4.0MPa；Water/gas：1.80；Dry gas air speed：3000h-1；H2S contents：0.3%；
Time：100h.
Claims (10)
1. one kind carbonization Si modification sulfur-resistant transformation catalyst, it is characterised in that：Include the chemical composition of following mass ratio：
A kind of 2. preparation method of the carbonization Si modification sulfur-resistant transformation catalyst described in claim 1, it is characterised in that：Including such as
Lower step：
(1) first, aluminum contained compound, magnesium-containing compound and titanium-containing compound are well mixed, then, add carborundum, oxidation
After silicon and active carbon powder mix, ball mill ball milling is put into 1~2 hour, add binding agent and be well mixed to obtain mixture；
(2) it is ammonium molybdate is soluble in water, it is added in the mixture that step (1) obtains, mediates；
(3) it is cobalt nitrate and magnesium nitrate is soluble in water, it is added in the mixture after the kneading that step (2) obtains, mediates again；
(4) the mixture extrusion forming after the kneading again for obtaining step (3), dries, roasting, obtains finished catalyst.
3. the preparation method of carbonization Si modification sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：Described
Aluminum contained compound, magnesium-containing compound and titanium-containing compound are powdered.
4. the preparation method of carbonization Si modification sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：Described
Aluminum contained compound is boehmite, aluminum oxide or aluminium glue.
5. the preparation method of carbonization Si modification sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：Described
Magnesium-containing compound is magnesia, magnesium oxalate, magnesium carbonate or magnesium stearate.
6. the preparation method of carbonization Si modification sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：Described
Titanium-containing compound is metatitanic acid or titanium oxide.
7. the preparation method of carbonization Si modification sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：Described
Carborundum is porous silicon carbide, is not less than 150m than surface2/g。
8. the preparation method of carbonization Si modification sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：Described
Activated carbon is wood activated charcoal, is not less than 300m than surface2/g。
9. the preparation method of carbonization Si modification sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：Described
Binding agent is two or more the mixture in starch, sucrose, sesbania powder, citric acid or oxalic acid.
10. the preparation method of carbonization Si modification sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：It is described
Sintering temperature be 500~800 DEG C, the time is 2~6h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101879451A (en) * | 2009-05-07 | 2010-11-10 | 中国石油化工股份有限公司 | Low-temperature Claus tail-gas hydrogenation catalyst and preparation method thereof |
| CN103769116A (en) * | 2012-10-20 | 2014-05-07 | 中国石油化工股份有限公司 | Sulfur tolerant shift catalyst and preparation method |
| CN104549336A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Activated carbon-based sulfur tolerant shift catalyst and preparation method thereof |
| WO2016096447A1 (en) * | 2014-12-19 | 2016-06-23 | Haldor Topsøe A/S | A method for removing hydrogen sulfide from an acid gas |
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2016
- 2016-08-29 CN CN201610749557.4A patent/CN107774288B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101879451A (en) * | 2009-05-07 | 2010-11-10 | 中国石油化工股份有限公司 | Low-temperature Claus tail-gas hydrogenation catalyst and preparation method thereof |
| CN103769116A (en) * | 2012-10-20 | 2014-05-07 | 中国石油化工股份有限公司 | Sulfur tolerant shift catalyst and preparation method |
| CN104549336A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Activated carbon-based sulfur tolerant shift catalyst and preparation method thereof |
| WO2016096447A1 (en) * | 2014-12-19 | 2016-06-23 | Haldor Topsøe A/S | A method for removing hydrogen sulfide from an acid gas |
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