CN107552061A - Activated carbon base sulfur-resistant transformation catalyst and preparation method thereof - Google Patents
Activated carbon base sulfur-resistant transformation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN107552061A CN107552061A CN201610504919.3A CN201610504919A CN107552061A CN 107552061 A CN107552061 A CN 107552061A CN 201610504919 A CN201610504919 A CN 201610504919A CN 107552061 A CN107552061 A CN 107552061A
- Authority
- CN
- China
- Prior art keywords
- activated carbon
- preparation
- transformation catalyst
- carbon base
- resistant transformation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention belongs to sulphur-resistant conversion converter technique field, and in particular to a kind of activated carbon base sulfur-resistant transformation catalyst and preparation method thereof.Include the component of following weight fraction：Al2O34~7%, CaO 2~3%, C 77~85%, CoO 2~4%, MoO27~9%.The present invention also provides its preparation method, carrier is prepared using activated carbon, boehmite, calcium hydroxide, then cobalt active component of cobalt is impregnated, the sulfur-resistant transformation catalyst intensity prepared is high, activity is good, long lifespan, stable performance, and the ability of the harsh operating mode such as energy high temperature resistant, high-speed.
Description
Technical field
The invention belongs to sulphur-resistant conversion converter technique field, and in particular to a kind of activated carbon base sulfur-resistant transformation catalyst and its
Preparation method.
Background technology
CO transformationreations are the important steps using coal as waste unstripped gas, and the reaction is the catalysis in transformation catalyst
Lower to carry out, common transformation catalyst has Fe-Cr HTS, copper system and cobalt molybdenum system with active component division, and wherein cobalt molybdenum system is with it
Wide active warm area, energy resistant to sulfur, have the advantages that preferable mithridatism is most widely used.Domestic Co-Mo sulfur-tolerant shift catalyst typically with
Cobalt molybdenum is active component, using magnalium titanium as carrier, adds the auxiliary agent such as rare earth, industrially comparative maturity.
Activated carbon has the characteristics that highly developed pore structure, huge specific surface area, stable chemical property, huge
Specific surface area be advantageous to the scattered of active component, flourishing pore structure is advantageous to the progress of reaction, stable chemical property
Be advantageous to extend catalyst life, the interaction between activated carbon and metal active constituent is weak in addition, is advantageous to improve activity
The state of cure (vulcanization) of component, the excellent absorption property of activated carbon are advantageous to the absorption to hydrogen sulfide, strengthen the energy of resistance to low-sulfur of catalyst
Power.Thus activated carbon is a kind of good support material, but activated carbon is difficult to be molded, intensity difference, does not reach sulphur-resistant conversion catalysis
The application requirement of agent, being one needs to solve the problems, such as.
Prior art yet there are no solves strength problem using adhoc approach, and patent CN201310480400 is related to a kind of activity
Charcoal base sulfur-resistant transformation catalyst and preparation method thereof, using activated carbon Quito system carrier structure, also contain magnalium titanium in carrier
Compound, using nickel and molybdenum as active constituent, alkali metal is coagent, the preparation side being combined using coprecipitation and kneading method
Method；Patent CN201310481410 is related to a kind of high activity and high stability sulfur-resistant transformation catalyst and preparation method thereof, with nickel, cobalt
With molybdenum ternary component as active component；Using activated carbon as carrier, aluminum oxide is prepared as carrier auxiliary agent using kneading method；
Patent CN201310482146 is related to a kind of magnalium charcoal complex carrier sulfur-resistant transformation catalyst and preparation method thereof, using magnalium charcoal
Complex carrier structure, wherein magnalium component exist with magnesium aluminate spinel phase structure, and active component is selected from cobalt nitrate and ammonium molybdate
Binary composition, prepared using kneading method.Above patent is not directed to use calcium hydroxide.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of activated carbon base sulfur-resistant transformation catalyst, intensity
High, active good, long lifespan, stable performance, and the ability of the harsh operating mode such as energy high temperature resistant, high-speed；The present invention also provides it
Preparation method.
Activated carbon base sulfur-resistant transformation catalyst of the present invention, include the component of following weight fraction：
Al2O3：4~7%
CaO：2~3%
C：77~85%
CoO：2~4%
MoO2：7~9%.
The preparation method of activated carbon base sulfur-resistant transformation catalyst of the present invention, comprises the following steps：
(1) by Ca (OH)2The aqueous solution is placed in reactor, is put into activated carbon, boehmite, leads to titanium dioxide while stirring
Carbon, after by material filtering, the sediment after being filtered,
(2) sediment is dried, is placed in after crushing in kneader, add the mixed liquor of water and the concentrated sulfuric acid, mediated, extrusion,
Dry, be calcined, obtain carrier；
(3) ammonia solvent cobalt nitrate and ammonium heptamolybdate are used, dipping solution is made, the carrier that then impregnation steps (2) obtain,
Naturally dry, finished product is obtained after roasting.
Ca(OH)2The aqueous solution is：By Ca (OH)2Powder is positioned in water, is kept 10 DEG C of constant temperature, stratification after stirring, is taken
Its supernatant.
Wherein：
Drying temperature is 110~130 DEG C in step (2).
750 DEG C~950 DEG C 2~3h of roasting under anoxic condition are roasted in step (2).
450 DEG C~550 DEG C 2~3h of roasting under anoxic condition are roasted in step (3).
Add the 2-2.2mL concentrated sulfuric acids in every 100mL water in the mixed liquor of step (2) reclaimed water and the concentrated sulfuric acid.
The ratio of ammoniacal liquor, cobalt nitrate and ammonium heptamolybdate is 40-80 in step (3)：6.5-13：6.2-12.4 ammoniacal liquor is with mL
Meter, cobalt nitrate and ammonium heptamolybdate are in terms of g.
Preferably, the preparation method of activated carbon base sulfur-resistant transformation catalyst of the present invention, comprises the following steps：
(1) by Ca (OH)2Powder is positioned in water, is kept 8-12 DEG C of constant temperature, stratification after stirring, is taken its supernatant,
It is placed in the reactor at same temperature, activated carbon, boehmite is put into wherein, stirs 5~15 minutes, then side stirring
Side leads to carbon dioxide, after 100~140 minutes, stops stirring, mixed material in kettle is released and filtered, heavy after being filtered
Starch；
(2) sediment is crushed to not less than 200 mesh, is placed in kneader, add water and dense in 110~130 DEG C of drying
The mixed liquor of sulfuric acid, mediate 30~50 minutes, extrusion, dry, 750 DEG C~950 DEG C 2~3h of roasting, are obtained under anoxic condition
Carrier；
(3) ammonia solvent cobalt nitrate and ammonium heptamolybdate are used, dipping solution is made, then gained in equivalent impregnation step (2)
Carrier, naturally dry, under anoxic condition 450 DEG C~550 DEG C roasting 2~3h, obtain finished product.
In summary, the present invention has advantages below：
(1) present invention prepares carrier using activated carbon, boehmite, calcium hydroxide, then impregnates cobalt active component of cobalt,
The sulfur-resistant transformation catalyst intensity prepared is high, active good, stable performance, and can the harsh operating mode such as high temperature resistant, high-speed
Ability.
(2) present invention is prepared using activated carbon, boehmite, calcium hydroxide and carried using activated carbon as main carrier components
Body, the problem of overcoming existing absorbent charcoal carrier low intensity, intensity is high, and activity is good, long lifespan, stable performance, can high temperature resistant, height
The harsh operating mode such as air speed, suitable for sulphur-resistant conversion technical field.
Embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
By 500g Ca (OH)2It is positioned in container, adds 2Kg deionized waters, 10 DEG C of constant temperature, stood after stirring, is layered,
Take supernatant liquor 1Kg to be positioned in reactor, add 3.8g boehmites, 46g activated carbons, after stirring 10 minutes, side stirring
While being passed through carbon dioxide, after reacting 2h, release mixture and filter, the sediment after being filtered.
Sediment is dried at 120 DEG C, is crushed to not less than 200 mesh, is placed in kneader, takes 150ml water, is added
The 3ml concentrated sulfuric acids, water is poured into kneader, is mediated 30 minutes, extrusion, is dried, and 800 DEG C of roasting 3h, are obtained under anoxic condition
Carrier.
6.5g cobalt nitrates and 6.2g ammonium heptamolybdates are positioned in 40ml ammoniacal liquor, form complex solution, equivalent impregnation is above-mentioned
Carrier, naturally dry, 530 DEG C of roasting 3h, obtain finished catalyst, numbering C-1 under anoxic condition.
Embodiment 2
By 400g Ca (OH)2It is positioned in container, adds 3Kg deionized waters, 10 DEG C of constant temperature, stood after stirring, is layered,
Take supernatant liquor 2Kg to be positioned in reactor, add 7.6g boehmites, 92g activated carbons, after stirring 10 minutes, side stirring
While being passed through carbon dioxide, after reacting 1.8h, release mixture and filter, the sediment after being filtered.
Sediment is dried at 125 DEG C, is crushed to not less than 200 mesh, is placed in kneader, takes 300ml water, is added
The 6ml concentrated sulfuric acids, water is poured into kneader, is mediated 50 minutes, extrusion, is dried, and 900 DEG C of roasting 2.5h, are obtained under anoxic condition
To carrier.
13g cobalt nitrates and 12.4g ammonium heptamolybdates are positioned in 80ml ammoniacal liquor, form complex solution, equivalent impregnation is above-mentioned
Carrier, naturally dry, 550 DEG C of roasting 2.5h, obtain finished catalyst, numbering C-2 under anoxic condition.
Embodiment 3
By 400g Ca (OH)2It is positioned in container, adds 2Kg deionized waters, 10 DEG C of constant temperature, stood after stirring, is layered,
Take supernatant liquor 1Kg to be positioned in reactor, add 5.6g boehmites, 43g activated carbons, after stirring 10 minutes, side stirring
While being passed through carbon dioxide, after reacting 2.3h, release mixture and filter, the sediment after being filtered.
Sediment is dried at 110 DEG C, is crushed to not less than 200 mesh, is placed in kneader, takes 150ml water, is added
The 3ml concentrated sulfuric acids, water is poured into kneader, is mediated 40 minutes, extrusion, is dried, and 750 DEG C of roasting 2h, are obtained under anoxic condition
Carrier.
8.7g cobalt nitrates and 7.0g ammonium heptamolybdates are positioned in 40ml ammoniacal liquor, form complex solution, equivalent impregnation is above-mentioned
Carrier, naturally dry, 500 DEG C of roasting 2h, obtain finished catalyst, numbering C-3 under anoxic condition.
Embodiment 4
By 300g Ca (OH)2It is positioned in container, adds 3Kg deionized waters, 10 DEG C of constant temperature, stood after stirring, is layered,
Take supernatant liquor 1.5Kg to be positioned in reactor, add 4.8g boehmites, 71g activated carbons, after stirring 10 minutes, while stirring
Mix side and be passed through carbon dioxide, after reacting 1.7h, release mixture and filter, the sediment after being filtered.
Sediment is dried at 130 DEG C, is crushed to not less than 200 mesh, is placed in kneader, takes 230ml water, is added
The 5ml concentrated sulfuric acids, water is poured into kneader, is mediated 35 minutes, extrusion, is dried, and 950 DEG C of roasting 2.8h, are obtained under anoxic condition
To carrier.
6.5g cobalt nitrates and 8.1g ammonium heptamolybdates are positioned in 60ml ammoniacal liquor, form complex solution, equivalent impregnation is above-mentioned
Carrier, naturally dry, 400 DEG C of roasting 2.4h, obtain finished catalyst, numbering C-4 under anoxic condition.
The catalyst that embodiment 1-4 is prepared carries out intensity and pressurization active testing, test result are shown in Table 1.
The intensity and activity for the catalyst that the embodiment 1-4 of table 1 is prepared
Claims (9)
- A kind of 1. activated carbon base sulfur-resistant transformation catalyst, it is characterised in that：Include the component of following weight fraction：Al2O3：4~7%CaO：2~3%C：77~85%CoO：2~4%MoO2：7~9%.
- A kind of 2. preparation method of the activated carbon base sulfur-resistant transformation catalyst described in claim 1, it is characterised in that：Including following Step：(1) by Ca (OH)2The aqueous solution is placed in reactor, is put into activated carbon, boehmite, leads to carbon dioxide while stirring, complete By material filtering after finishing, the sediment after being filtered；(2) sediment is dried, is placed in after crushing in kneader, add the mixed liquor of water and the concentrated sulfuric acid, mediated, extrusion, dry, Roasting, obtains carrier；(3) ammonia solvent cobalt nitrate and ammonium heptamolybdate are used, dipping solution is made, the carrier that then impregnation steps (2) obtain is natural Dry, finished product is obtained after roasting.
- 3. the preparation method of activated carbon base sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：Ca(OH)2Water Solution is：By Ca (OH)2Powder is positioned in water, is kept 10 DEG C of constant temperature, stratification after stirring, is taken its supernatant.
- 4. the preparation method of activated carbon base sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：Step (2) Middle drying temperature is 110~130 DEG C.
- 5. the preparation method of activated carbon base sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：Step (2) In be roasted under anoxic condition 750 DEG C~950 DEG C 2~3h of roasting.
- 6. the preparation method of activated carbon base sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：Step (3) In be roasted under anoxic condition 450 DEG C~550 DEG C 2~3h of roasting.
- 7. the preparation method of activated carbon base sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：Step (2) Add the 2-2.2mL concentrated sulfuric acids in every 100mL water in the mixed liquor of reclaimed water and the concentrated sulfuric acid.
- 8. the preparation method of activated carbon base sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：Step (3) The ratio of middle ammoniacal liquor, cobalt nitrate and ammonium heptamolybdate is 40-80：6.5-13：6.2-12.4, ammoniacal liquor is in terms of mL, cobalt nitrate and seven molybdenums Sour ammonium is in terms of g.
- 9. the preparation method of activated carbon base sulfur-resistant transformation catalyst according to claim 2, it is characterised in that：(1) by Ca (OH)2Powder is positioned in water, is kept 8-12 DEG C of constant temperature, stratification after stirring, is taken its supernatant, is placed in same In reactor at a temperature of sample, activated carbon, boehmite are put into wherein, stirs 5~15 minutes, then leads to two while stirring Carbonoxide, after 100~140 minutes, stop stirring, mixed material in kettle is released and filtered, the sediment after being filtered；(2) sediment is dried at 110~130 DEG C, is crushed to not less than 200 mesh, is placed in kneader, add water and the concentrated sulfuric acid Mixed liquor, mediate 30~50 minutes, extrusion, dry, under anoxic condition 750 DEG C~950 DEG C roasting 2~3h, obtain carrier；(3) ammonia solvent cobalt nitrate and ammonium heptamolybdate are used, dipping solution is made, then the load of the middle gained of equivalent impregnation step (2) Body, naturally dry, 450 DEG C~550 DEG C 2~3h of roasting, obtain finished product under anoxic condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610504919.3A CN107552061A (en) | 2016-06-30 | 2016-06-30 | Activated carbon base sulfur-resistant transformation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610504919.3A CN107552061A (en) | 2016-06-30 | 2016-06-30 | Activated carbon base sulfur-resistant transformation catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107552061A true CN107552061A (en) | 2018-01-09 |
Family
ID=60968521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610504919.3A Pending CN107552061A (en) | 2016-06-30 | 2016-06-30 | Activated carbon base sulfur-resistant transformation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107552061A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1602998A (en) * | 2004-03-16 | 2005-04-06 | 潍坊联信化学有限公司 | Catalyst for improving organic sulfur hydrolysis rate, its carrier and preparation method |
| CN101143325A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院大连化学物理研究所 | Method for preparing catalyst and application thereof |
| CN101199933A (en) * | 2006-12-16 | 2008-06-18 | 汤海溶 | Polynary metal oxide catalyst and preparing process thereof |
| CN101862684A (en) * | 2010-05-07 | 2010-10-20 | 大连理工大学 | Aluminum oxide-activated carbon composite carrier, preparation method and prepared catalyst |
| CN102593473A (en) * | 2012-02-14 | 2012-07-18 | 中国科学院长春应用化学研究所 | Fuel cell catalyst and preparation method thereof |
| CN104549326A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | High activity and high stability sulfur-tolerant shift catalyst and preparation method thereof |
| CN104549324A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Magnesium-aluminum-carbon composite support sulfur-tolerant shift catalyst and preparation method thereof |
| CN104986785A (en) * | 2015-06-17 | 2015-10-21 | 中国石油天然气集团公司 | Large-specific-surface-area mesoporous divalent metal aluminum base spinel and preparing method and application thereof |
| CN105251502A (en) * | 2014-12-02 | 2016-01-20 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Mercury-free catalyst for acetylene hydrochlorination |
| CN105854888A (en) * | 2016-04-15 | 2016-08-17 | 西安向阳航天材料股份有限公司 | Copper-based low-temperature conversion catalyst and preparation method thereof |
-
2016
- 2016-06-30 CN CN201610504919.3A patent/CN107552061A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1602998A (en) * | 2004-03-16 | 2005-04-06 | 潍坊联信化学有限公司 | Catalyst for improving organic sulfur hydrolysis rate, its carrier and preparation method |
| CN101143325A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院大连化学物理研究所 | Method for preparing catalyst and application thereof |
| CN101199933A (en) * | 2006-12-16 | 2008-06-18 | 汤海溶 | Polynary metal oxide catalyst and preparing process thereof |
| CN101862684A (en) * | 2010-05-07 | 2010-10-20 | 大连理工大学 | Aluminum oxide-activated carbon composite carrier, preparation method and prepared catalyst |
| CN102593473A (en) * | 2012-02-14 | 2012-07-18 | 中国科学院长春应用化学研究所 | Fuel cell catalyst and preparation method thereof |
| CN104549326A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | High activity and high stability sulfur-tolerant shift catalyst and preparation method thereof |
| CN104549324A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Magnesium-aluminum-carbon composite support sulfur-tolerant shift catalyst and preparation method thereof |
| CN105251502A (en) * | 2014-12-02 | 2016-01-20 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Mercury-free catalyst for acetylene hydrochlorination |
| CN104986785A (en) * | 2015-06-17 | 2015-10-21 | 中国石油天然气集团公司 | Large-specific-surface-area mesoporous divalent metal aluminum base spinel and preparing method and application thereof |
| CN105854888A (en) * | 2016-04-15 | 2016-08-17 | 西安向阳航天材料股份有限公司 | Copper-based low-temperature conversion catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MELIS S. DUYAR ET AL.: ""In Situ CO2 Capture Using CaO/γ-Al2O3 Washcoated Monoliths for Sorption Enhanced Water Gas Shift Reaction"", 《IND. ENG.CHEM. RES.》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104888798B (en) | A kind of high activated catalyst for rich CO gas sulfur-tolerance deoxidation and preparation method thereof | |
| CN102600860B (en) | Catalyst suitable for complete methanation of middle-low-temperature synthetic gas and preparation method thereof | |
| CN103480375A (en) | Carbon monoxide methanating catalyst and preparation method thereof | |
| CN104248961A (en) | Sulfur-tolerant shift catalyst and preparation method thereof | |
| CN106902814A (en) | One kind catalysis burning order mesoporous integral catalyzer of rare earth base and preparation method thereof | |
| CN103316691A (en) | Magnetic solid acid and preparation method thereof | |
| CN109912372A (en) | Synthesis gas methanation catalyst and its preparation method | |
| CN106512984A (en) | Preparation method of high-activity diesel hydrodesulfurization catalyst | |
| CN102773108B (en) | Preparation method of catalyst for preparing hydrogen from hydrogen sulfide | |
| CN109395770A (en) | A kind of iron-based hydrogenation catalyst and preparation method thereof | |
| Chen et al. | Three-dimensionally ordered macro–mesoporous CoMo bulk catalysts with superior performance in hydrodesulfurization of thiophene | |
| CN104624197B (en) | Deoxygenating and desulfurization double-function fine desulfurization agent and preparation method thereof | |
| CN103447094A (en) | Preparation method of desulfurization catalyst | |
| CN106552640A (en) | Reformer feed catalyst for pre-hydrogenation and preparation method thereof | |
| CN102949997B (en) | Catalyst-absorbent complex for absorbing and strengthening low-carbon hydrocarbon steam reforming hydrogen and preparing method of complex | |
| CN101402041B (en) | Self-heating conversion catalyst rich in methane gas and method of producing the same | |
| CN107552061A (en) | Activated carbon base sulfur-resistant transformation catalyst and preparation method thereof | |
| CN104971731B (en) | A kind of wide warm sulfur-resistant transformation catalyst and preparation method thereof | |
| CN106964363A (en) | A kind of anti-arsenic CO sulfur-resistant transformation catalysts and preparation method | |
| CN104549326A (en) | High activity and high stability sulfur-tolerant shift catalyst and preparation method thereof | |
| CN103157518A (en) | Mesoporous magnesium oxide, hydrodesulfurization catalyst loading CoMo metal sulfide and application thereof | |
| CN108097237A (en) | Modified manganese sand, its conversion methanation catalyst and preparation method as carrier | |
| CN103223341A (en) | Preparation method of novel hydro-desulfurization catalyst | |
| CN104549337B (en) | Oxidation catalyst for mercaptan in light oil, as well as preparation method and application of mercaptan oxidation catalyst | |
| CN102151574B (en) | Novel CO sulfur-tolerant shift catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180109 |
|
| RJ01 | Rejection of invention patent application after publication |