CN103769234B - Protective agent of sulfur-resistant transformation catalyst and preparation method thereof - Google Patents
Protective agent of sulfur-resistant transformation catalyst and preparation method thereof Download PDFInfo
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- CN103769234B CN103769234B CN201210404435.3A CN201210404435A CN103769234B CN 103769234 B CN103769234 B CN 103769234B CN 201210404435 A CN201210404435 A CN 201210404435A CN 103769234 B CN103769234 B CN 103769234B
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Abstract
The protective agent of a kind of sulfur-resistant transformation catalyst of the present invention; comprise carrier and active component; it is characterized in that with attapulgite clay be main carrier material; the pulverulent solids compound containing magnesium is added in carrier; active component is copper, nickel binary composition; and adding coagent, coagent is one or more in zinc oxide, iron oxide, chromium oxide, zirconia or its corresponding solubility salt.The present invention adopts kneading method to be prepared from, raw materials used employing wide material sources, attapulgite clay with low cost, not only preparation technology is simple, and cost is low, has well adsorb detoxification to the poisonous substance such as arsenic (As), hydrogen cyanide, carbonyls of sulfur-resistant transformation catalyst.Can be used for high pressure, high-speed, high WGR harsh conditions, to ash content and poisonous substance high adsorption capacity in the heavy charge preparing synthetic gas such as residual oil, heavy oil, petroleum coke, coal, can available protecting main transformer catalyst changeout, extend main transformer catalyst service life.
Description
Technical field
The invention belongs to sulphur-resistant conversion technical field, be specifically related to a kind of protective agent and preparation method of sulfur-resistant transformation catalyst.
Background technology
Co-Mo sulfur-tolerant wide temperature shift catalyst is mainly for meeting the needs producing unstripped gas with heavy charges such as heavy oil, residual oil, coals, its 100-150 DEG C lower than iron system high temperature conversion catalyst light-off temperature, even just demonstrate excellent activity at 160 DEG C, suitable with copper system low temperature conversion catalyst, and its heat resistance is suitable with Fe-Cr HTS high temperature conversion catalyst, therefore there is very wide active warm area, nearly cover iron system high temperature conversion catalyst and the whole active warm area of copper system low temperature conversion catalyst.In recent years, along with the rise of crude oil price, Coal Chemical Industry obtains and develops on a large scale very much, and its gasifying process is also constantly being weeded out the old and bring forth the new.Due to the at present both at home and abroad diversity of coal gasifying process and the well sold and in short supply gradually of coal resource, the kind of coal and product follow-up coal gasifying process of verifying also result in very large impact.A small amount of impurity contained in process gas, as: arsenic (As), hydrogen cyanide, carbonyls etc., after washing removes, nubbin enters transformation system, accumulates over a long period to making a big impact the service life of transformation catalyst.Especially the colm that ash content is larger brings huge challenge to subsequent purification technique, and sulfur-resistant transformation catalyst also inevitably faces the problem of band water-band ash simultaneously, and its applying working condition worsens further.For this reason, many research units all developed protective agent for the protection of Co-Mo sulfur-tolerant shift catalyst or detoxifying agent in recent years, and technological design unit also increases detoxification groove and protects transformation catalyst with this before transformation system, extending catalyst service life.But catalyst used is at present main mainly with magnalium system, aluminium oxide greatly, and active component is in the majority with cobalt molybdenum, there is the shortcomings such as expensive, antitoxin and protective value is poor.
The attapulgite resource of China occupies the monopoly position of more than 70% in the world, but current exploitation and scientific research aspect but allow of no optimist, and are substantially still in the primary stage of selling resource.The processing factory of considerable part attapulgite, ubiquity the extensive problem of exploitation processing, mainly produces the primary product that the technology contents such as exterior coating, compound fertilizer binding agent and feed addictive are lower, and price per ton only has tens to dozens of yuan, product lacks scientific and technological content, and added value is low.A kind of clay mineral that it is key component that Concave-convex clay rod refers to attapulgite (attapulgite).Attapulgite is a kind of crystalloid hydrous magnesium aluminium silicate mineral, has unique layer chain structure feature, in its structure, there is crystal lattice, the Na containing non-quantitative in crystal
+, Ca
2+, Fe
3+, Al
3+, crystal is needle-like, threadiness or fiber collection shape.Attapulgite has unique dispersion, high temperature resistant, anti-good colloidal nature and the higher adsorption bleaching ability such as saline and alkaline, and has certain plasticity and cohesive force, and its chemical equation is: Mg
5si
8o
20 (OH)
2(OH) 4H
2o, wherein Mg is often replaced by Al and Fe.Concave-convex clay rod aggregate is earthy block configuration, and color is canescence, steel gray, micro-Huang or light green, greasy luster, and density is less, mohs hardness 2-3 level, be viscosity and plasticity time moist, dry contraction is little, and does not produce be full of cracks, water imbibition is strong, can reach about more than 150%, pH=8.5.Due to internal porous road, specific area is large, can reach 350m
2/ more than g.Attapulgite clay mineral has the attribute of nano material; it is the natural nano structure mineral material with nanochannel structure; because they have very large specific area and certain ion exchangeable; therefore drier, anti-blushing agent, adsorbent, catalyst carrier and carrier etc. are widely used as, but for the protectant research of sulphur-resistant conversion with report less.
Chinese patent CN102198401A relates to one attapulgite to be done carrier and prepares cobalt molybdenum CO sulfur-resistant transformation catalyst and method thereof, and applies it in CO transformationreation.Adopt the method for dipping-precipitation by the oxide of nanoscale or its salt dopping in acid-treated attapulgite, prepare recessed native active catalyst support, flood cobalt active component of cobalt afterwards and prepare cobalt molybdenum system CO sulfur-resistant transformation catalyst.Simple to operate in preparation process, abundant raw material is easy to get, and recessed native carrier is relative to commercial active carbon, γ-Al
2o
3, MgAl
2o
4cheap in carrier, there is larger commercial Application meaning.But this patent is sulfur-resistant transformation catalyst preparation method, there is the problems such as water consumption is large, difficult containing sour water, preparation section is complicated.
Chinese patent CN201010584555 relates to a kind of preparation method of adsorbing carbon dioxide efficiently modified attapulgite clay adsorbing material.Sorbing material, primarily of Concave-convex clay rod, alkali metal or alkaline earth oxide modifier composition, is made through operations such as dipping, oven dry and roastings.This sorbing material has good absorption purifying effect to carbon dioxide, have simultaneously active high, cost is low, high adsorption capacity, adsorption capacity are large and the renewable advantage such as to recycle.This invention is mainly adsorbed carbon dioxide, can not be used for sulfur resistant conversion process.
Chinese patent CN100430140C relates to a kind of preparation method protecting the counterpoison of cobalt molybdenum co surfer-resistant shift catalyst.The method is by active carrier γ-Al
2o
3with ammonium molybdate, with a kind of soluble cobalt being selected from cobalt nitrate, cobalt chloride, cobalt acetate, cobaltous sulfate, be selected from a redox materials solution for nitric acid, nitrous acid, thiosulfuric acid, hydrogen peroxide, and the maceration extract that ammonia spirit is made into carries out total immersion, dipping post-drying i.e. obtained product.In its maceration extract, cobalt salt counts 1.2 ± 0.1% with C ο O, and ammonium molybdate is 7 ± 0.1%, and ammonia vol is 1% ~ 5%, and redox materials solution concentration counts 1% ~ 15% with maceration extract.Counterpoison prepared by this law can protect the activity of cobalt molybdenum co surfer-resistant shift catalyst, thus guarantees the normal operation of catalyst.This protective agent adopts cobalt molybdenum to be active component, γ-Al
2o
3for active carrier, preparation cost is high.
Chinese patent CN1051384 relates to a kind of adsorbent and the method for making thereof of protecting transformation catalyst, and this adsorbent for main component, take hydrated alumina as bonding agent, NH with refining porous mineral material bentonite or sepiolite, diatomite, natural zeolite
4hCO
3or NH
4nO
3for additive, mix shaping, drying, heat-activated obtains the granule adsorbent of pore volume 0.30 ~ 0.54 ml/g.More cheap than transformation catalyst nearly 10 times of this adsorbent; as the preposition protective layer of transformation catalyst in Ammonia Production, conversion gas is purified, decreases in gas harmful components to the direct toxicity of catalyst; thus can service life of extending catalyst, obtain good economic benefit.This patent, for adding active component, is only protected by adsorption method, limited to transformation catalyst protective capability.
Chinese patent CN101249417 relates to a kind of Concave-convex clay rod-aluminium hydroxide/iron nano-compound adsorbent, its preparation method and application, it is characterized in that by nano combined, at Features of Attapulgite Minerals area load aluminium hydroxide or load aluminium and iron hydroxide mixture, by weight percentage, aluminium hydroxide or aluminium and the content of iron hydroxide mixture in adsorbent are 5-50%; In aluminium and iron hydroxide mixture, the content of aluminium hydroxide is not less than iron hydroxide.Compound adsorbent of the present invention has high-adsorption-capacity to phosphorus, As, F in water, may be used for the process of the advanced treating dephosphorization of sewage treatment plants draining, eutrophication water dephosphorization, high arsenic or high fluorine groundwater.This patent is mainly used in sanitary sewage absorption.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of protective agent and preparation method of sulfur-resistant transformation catalyst; make full use of the physico-chemical property of attapulgite clay itself; add nickel, copper activity component simultaneously; to improve the adsorption capacity of the impurity that to grade to poisonous substance and ash, available protecting subsequent conversion catalyst.
The protective agent of a kind of sulfur-resistant transformation catalyst of the present invention; comprise carrier and active component; it is characterized in that with attapulgite clay be main carrier material; the pulverulent solids compound containing magnesium is added in carrier; active component is copper, nickel binary composition; and adding coagent, coagent is one or more in zinc oxide, iron oxide, chromium oxide, zirconia or its corresponding solubility salt.
Better adsorb protected effect for having under the process conditions of harshness, described sulphur-resistant conversion protective agent portion of techniques index is as follows:
For adapting to sulphur-resistant conversion high pressure, high-speed, high WGR stringent process conditions, fresh protective agent intensity should be greater than 170N/cm, and hydro-thermal and poach strength retention ratio are not less than 80%;
For increasing the adsorption capacity of protective agent to sulfur resistant conversion process gas impurity and poisonous substance, pore volume should be greater than 0.3cm
3/ g; Specific area should be greater than 150m
2/ g.
The protective agent of sulfur-resistant transformation catalyst of the present invention makes full use of the characteristic of attapulgite clay, and for preparation intensity is high, specific area is large, pore volume is large, efficient sulphur-resistant conversion protective agent provides the basis of the structure of matter.
Preferred technical scheme is as follows:
In mass percentage, be made up of following raw material, each raw material total amount is 100%:
Active component is copper, nickel binary composition, and copper metal oxide content is 1.5-8.0% (m/m), preferred 3-6.0% (m/m); Nickel metal oxide content is 2.0-7%(m/m), preferred 3.0-6.0% (m/m), and copper, nickel total content are no more than 12% (m/m).The nitrate of preferred use copper, nickel is as raw material.
Coagent content is 0.5-3%(m/m), best 1-2%(m/m);
Be 1-15%(m/m containing the pulverulent solids compound of magnesium by magnesia content);
Expanding agent content is 1-6%(m/m), best 2-4%(m/m);
Binder content is 1-6%(m/m), best 2-4%(m/m);
Attapulgite clay is surplus.
Magnesia (MgO), silica (SiO in wherein said attapulgite clay
2) and aluminium oxide (Al
2o
3) total content lower than 70%, preferably should not be not less than 75%, water content is lower than 5%.
The described pulverulent solids compound containing magnesium is that magnesia, magnesium oxalate, magnesium carbonate, dolomol etc. contain magnesium solid, powdery compound, preferential oxidation magnesium.
Described expanding agent is polyvinyl alcohol, glucose field mountain valley with clumps of trees and bamboo powder, citric acid, starch, sucrose etc., preferred sesbania powder.
Described binding agent is acetic acid, citric acid, oxalic acid and nitric acid etc., optimization citric acid and/or oxalic acid.
The present invention adds a certain amount of copper, nickel active component, and adopt kneading method to be prepared from, not only preparation technology is simple, and cost is low, has well adsorb detoxification to the poisonous substance such as arsenic (As), hydrogen cyanide, carbonyls of sulfur-resistant transformation catalyst.And select suitable coagent and suitable active component feed postition, active component is scattered at carrier surface.Meanwhile, select suitable binding agent and expanding agent according to preparation technology, good with main body protective agent component compatibility, guarantee that protective agent has suitable intensity, pore structure and structural stability.
A kind of concrete preparation method is as follows for protective agent:
1, attapulgite clay is pulverized, then sieve.
2, solution preparation: to prepare 100 grams of protective agents,
Take a certain amount of copper nitrate and nickel nitrate is dissolved in 30-60ml deionized water, obtain solution A.
Take a certain amount of binding agent, solubility expanding agent and coagent to be added in 10-30ml deionized water, obtain solution B.Expanding agent herein, when adopting soluble ingredient, is prepared into solution.If during insolubility raw material, need not solution be prepared into, when next step is shaping, directly mix with carrier as siccative.
3, protective agent is shaping:
Take a certain amount of attapulgite clay, add and mix with a certain amount of pulverulent solids compound containing magnesium and insoluble expanding agent siccative; Add solution A, mediate evenly; Add solution B again, mediate evenly.Obtained protective agent finished product after shaping, dry, roasting.
As mentioned above, the expanding agent of step 2 and step 3, when expanding agent is soluble products, is prepared into solution in step 2 and uses.On the contrary, when expanding agent is insoluble powder, expanding agent siccative is added in step 3.
Wherein:
In step 1, concave convex rod clay powder is broken to more than 160 orders.160 orders and above granularity content are not less than 95%, are preferably not less than 98%; Preferably 180 orders and above granularity content are not less than 85%, are preferably not less than 90%.
The shaping sintering temperature of protective agent in step 3 is 400-600 DEG C, preferably 500 DEG C.
Protective agent outward appearance in step 3 can be bar shaped, clover, bunge bedstraw herb type and hollow bar shaped etc., preferred bar shaped.
Beneficial effect of the present invention:
This sulphur-resistant conversion protective agent has that intensity is high, structure and structural stability good; can be used for high pressure, high-speed, high WGR harsh conditions; service life is longer; to ash content and poisonous substance high adsorption capacity in the heavy charge preparing synthetic gas such as residual oil, heavy oil, petroleum coke, coal; can available protecting main transformer catalyst changeout, extend main transformer catalyst service life.Raw materials used employing wide material sources, attapulgite clay with low cost, and simplify preparation technology, greatly reduce catalyst preparing cost, simultaneously also for attapulgite clay comprehensive utilization searches out an effective way, there is good economic benefit and environmental benefit.
Accompanying drawing explanation
Fig. 1 is known catalyst pressurization activity rating device and schematic flow sheet.
In figure: 1. raw material gas purifying device; 2. pressure reducer; 3. blender; 4. Pressure gauge; 5. lockout valve; 6. heating furnace; 7. reaction tube; 8. thermocouples tube in pipe; 9. condenser; 10. separator; 11. drain pumps; 12. wet flow indicators; 13. vaporizers; 14. tanks; 15. water measuring pumps
Detailed description of the invention
Pressurization activity rating device and flow process are as shown in Figure 1.This device, for simulating industrial condition, under a certain pressure, measures " former granularity " catalyst tail gas carbonomonoxide concentration and change thereof at different conditions, compares the performances such as the shift activity of catalyst and stability, the properties of overall merit catalyst.Reaction tube is the stainless steel tube of Ф 45 × 5mm, and there are the thermocouples tube of Ф 8 × 2mm in central authorities.Before adopting certain synthetic ammonia workshop to convert, process gas is unstripped gas, allocates appropriate H into
2s, adds a certain amount of water according to the requirement of different WGR, after high-temperature gasification, enters reaction tube and carry out water gas shift reaction together with unstripped gas, tail gas chromatograph after reaction.
Pressurization appreciation condition is: unstripped gas forms, CO45 ~ 49%(V/V), CO
25 ~ 10%(V/V), H
2s > 0.05%(V/V), remaining is hydrogen; Dry gas air speed: 3000h
-1; Pressure: 4.0MPa; Evaluate inlet temperature: 250 DEG C; Catalyst loading amount: 50ml.
Embodiment 1
First attapulgite clay is dried 6h at 150 DEG C of temperature, then pulverize 180 mesh sieves.
Take 12.08g copper nitrate and 19.45g nickel nitrate is dissolved in 45ml deionized water, obtain solution A; Take 5.5g zirconium oxychloride, 1.0g citric acid and 3.0g oxalic acid to be added in 20ml deionized water, obtain solution B.
Take 79g attapulgite clay, 10.0g magnesia, 3.0g sesbania powder mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, roasting 3h at 530 DEG C, then Temperature fall is to room temperature.Namely finished product bar shaped sulphur-resistant conversion protective agent C-1 is obtained.Its intensity and strength stability thereof are in table 1.
Embodiment 2
First attapulgite clay is dried 10h at 110 DEG C of temperature, then pulverize 160 mesh sieves.
Take 4.53g copper nitrate and 23.34g nickel nitrate is dissolved in 45ml deionized water, obtain solution A; Take 4.1g zirconium oxychloride and 3.0g oxalic acid is added in 20ml deionized water, obtain solution B.
Take 76g attapulgite clay, 15.0g magnesia, 6.0g sesbania powder mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, roasting 4h at 420 DEG C, then Temperature fall is to room temperature.Namely finished product bunge bedstraw herb shape sulphur-resistant conversion protective agent C-2 is obtained.Its intensity and strength stability thereof are in table 1.
Embodiment 3
First attapulgite clay is dried 8h at 160 DEG C of temperature, then pulverize 160 mesh sieves.
Take 24.16g copper nitrate and 7.78g nickel nitrate is dissolved in 40ml deionized water, obtain solution A; Take 3.6g zinc nitrate and 3.0g oxalic acid is added in 20ml deionized water, obtain solution B.
Take 84g attapulgite clay, 5.0g magnesia, 3.0g sesbania powder mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, roasting 3h at 500 DEG C, then Temperature fall is to room temperature.Namely finished product bar shaped sulphur-resistant conversion protective agent C-3 is obtained.Its intensity and strength stability thereof are in table 1.
Embodiment 4
First attapulgite clay is dried 5h at 200 DEG C of temperature, then pulverize 180 mesh sieves.
Take 9.06g copper nitrate and 27.23g nickel nitrate is dissolved in 50ml deionized water, obtain solution A; Take 2.8g zirconium oxychloride, 4.0g sucrose and 3.0g citric acid to be added in 25ml deionized water, obtain solution B.
Take 88.0g attapulgite clay, 1.0g magnesia, 4.0g sesbania powder mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, roasting 2h at 600 DEG C, then Temperature fall is to room temperature.Namely finished product bar shaped sulphur-resistant conversion protective agent C-4 is obtained.Its intensity and strength stability thereof are in table 1.
Embodiment 5
First attapulgite clay is dried 12h at 150 DEG C of temperature, then pulverize 160 mesh sieves.
Take 18.12g copper nitrate and 11.67g nickel nitrate is dissolved in 40ml deionized water, obtain solution A; Take 5.3g chromic nitrate, 3.0g citric acid and 3.0g oxalic acid to be added in 25ml deionized water, obtain solution B.
Take 79.0g attapulgite clay, 10.0g magnesia, 3.0g glucose mixes, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, roasting 3h at 500 DEG C, then Temperature fall is to room temperature.Namely finished product cloverleaf pattern sulphur-resistant conversion protective agent C-5 is obtained.Its intensity and strength stability thereof are in table 1.
Embodiment 6
First attapulgite clay is dried 10h at 120 DEG C of temperature, then pulverize 160 mesh sieves.
Take 15.1g copper nitrate and 19.45g nickel nitrate is dissolved in 60ml deionized water, obtain solution A; Take 7.9g chromic nitrate and 3.0g oxalic acid is added in 25ml deionized water, obtain solution B.
Take 82.0g attapulgite clay, 5.0g magnesia, 4.0g sesbania powder mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, roasting 4h at 550 DEG C, then Temperature fall is to room temperature.Namely finished product bar shaped sulphur-resistant conversion protective agent C-6 is obtained.Its intensity and strength stability thereof are in table 1.
Embodiment 7
First attapulgite clay is dried 15h at 100 DEG C of temperature, then pulverize 160 mesh sieves.
Take 12.08g copper nitrate and 23.34g nickel nitrate is dissolved in 60ml deionized water, obtain solution A; Take 7.2g zinc nitrate and 3.0g oxalic acid is added in 25ml deionized water, obtain solution B.
Take 80.0g attapulgite clay, 8.0g magnesia, 2.0g sesbania powder mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, roasting 3h at 520 DEG C, then Temperature fall is to room temperature.Namely finished product bar shaped sulphur-resistant conversion protective agent C-7 is obtained.Its intensity and strength stability thereof are in table 1.
Embodiment 8
First attapulgite clay is dried 15h at 100 DEG C of temperature, then pulverize 160 mesh sieves.
Take 18.12g copper nitrate and 13.62g nickel nitrate is dissolved in 40ml deionized water, obtain solution A; Take 1.3g ferric nitrate, 2.0g sucrose and 2.0ml red fuming nitric acid (RFNA) to be added in 25ml deionized water, obtain solution B.
Take 84.0g attapulgite clay, 6.0g magnesia, 2.0g sesbania powder mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, roasting 4h at 450 DEG C, then Temperature fall is to room temperature.Namely finished product cloverleaf pattern sulphur-resistant conversion protective agent C-8 is obtained.Its intensity and strength stability thereof are in table 1.
Adopt poach, hydrothermal treatment consists strenuous test, investigate that protective agent boils through water at atmospheric pressure respectively, intensity after HTHP hydrothermal treatment consists and strength stability;
Boiling test condition: get a certain amount of protective agent and boil 5 hours in boiling water, measure the change of protective agent intensity after oven dry, to investigate protective agent intensity and stability thereof after hot-water soak at ambient pressure.
High-temperature high pressure water heat treatment test condition: in former granularity pressurization evaluating apparatus (as shown in Figure 1), with nitrogen and water vapour for medium, dry gas air speed: 4000h
-1; Pressure: 6.0MPa; Evaluate inlet temperature: 350 DEG C; Protective agent loading amount: 50.0ml; Liquid to steam ratio is process 100 hours under 1.8 conditions, measures the change of protective agent intensity after drying, and analoging industrial device harsh conditions, on the impact of catalyst performance, test rear intensity and stability thereof to investigate protective agent in harsh conditions.
The different syntheti c route of table 1 prepares protective agent intensity and strength stability contrast thereof
After adopting this protective agent, same industrial sulfur-resistant transformation catalyst QCS-03 pressurizes activity change rule as following table 2 after operation 200h.
Table 2 catalyst runs the active contrast of 200h pressurization
As can be seen from Table 2, after adopting protective agent of the present invention, activity preservation rate is all higher than not adding protectant blank test when running 100h for sulfur-resistant transformation catalyst QCS-03, and along with the prolongation of running time, activity preservation rate advantage is more obvious.
Claims (7)
1. the protective agent of a sulfur-resistant transformation catalyst, comprise carrier and active component, it is characterized in that with attapulgite clay be main carrier material, the pulverulent solids compound containing magnesium is added in carrier, active component is copper, nickel binary composition, and adding coagent, coagent is one or more in zinc oxide, iron oxide, chromium oxide, zirconia or its corresponding solubility salt;
Described protective agent, in mass percentage, is made up of following raw material, and each raw material total amount is 100%:
Copper metal oxide content is 1.5-8.0%, and nickel metal oxide content is 2.0-7%, and copper, nickel total content are no more than 12%,
The pulverulent solids compound of magnesium is 1-15% by magnesia content,
Coagent content is 0.5-3%,
Expanding agent content is 1-6%,
Binder content is 1-6%,
Attapulgite clay content is surplus,
In wherein said attapulgite clay, magnesia, silica and total content of alumina should not lower than 70%, and water content is lower than 5%.
2. protective agent according to claim 1, is characterized in that the described pulverulent solids compound containing magnesium is magnesia, magnesium oxalate, magnesium carbonate or dolomol.
3. protective agent according to claim 2, is characterized in that the described pulverulent solids compound containing magnesium is magnesia.
4. protective agent according to claim 1, is characterized in that described expanding agent is polyvinyl alcohol, glucose field mountain valley with clumps of trees and bamboo powder, citric acid, starch or sucrose; Described binding agent is acetic acid, citric acid, oxalic acid or nitric acid.
5. protective agent according to claim 1, it is characterized in that copper metal oxide content is 3-6.0%, nickel metal oxide content is 3.0-6.0%, and coagent content is 1-2%.
6. a protectant preparation method for sulfur-resistant transformation catalyst described in claim 1, is characterized in that comprising the steps:
(1) more than 160 orders, by attapulgite clay are crushed to,
(2), solution preparation: to prepare 100 grams of protective agents,
Take a certain amount of copper nitrate and nickel nitrate is dissolved in 30-60ml deionized water, obtain solution A;
Take a certain amount of binding agent, solubility expanding agent and coagent to be added in 10-30ml deionized water, obtain solution B;
(3), shaping:
Take attapulgite clay, add and mix containing the pulverulent solids compound of magnesium and insoluble expanding agent siccative, add solution A, mediate evenly, then add solution B, mediate evenly, through obtaining protective agent finished product after roasting at shaping, dry, 400-600 DEG C.
7. preparation method according to claim 6, is characterized in that protective agent outward appearance is bar shaped, clover, bunge bedstraw herb type or hollow bar shaped.
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| CN107233890A (en) * | 2017-07-27 | 2017-10-10 | 安徽理工大学 | A kind of nickel-base catalyst of attapulgite load of zinc modification and its preparation method and application |
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| CN112403480A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst and preparation method thereof |
| CN112403484B (en) * | 2019-08-23 | 2023-03-28 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst protective agent and preparation method thereof |
| CN114100695B (en) * | 2020-08-31 | 2023-10-20 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst protective agent and preparation method thereof |
| CN112916051B (en) * | 2021-01-25 | 2023-08-18 | 内蒙古中煤远兴能源化工有限公司 | Protective agent of sulfur-tolerant shift catalyst and preparation method thereof |
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| CN102198401A (en) * | 2011-04-08 | 2011-09-28 | 东南大学 | Cobalt molybdenum CO sulfur-tolerant shift catalyst by using attapulgite clay as carrier and its preparation method |
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| CN1051384A (en) * | 1990-12-10 | 1991-05-15 | 湖北省化学研究所 | The sorbent material and the method for making thereof of protection speed change catalyzer |
| CN101791579A (en) * | 2010-02-21 | 2010-08-04 | 湖北双雄催化剂有限公司 | Preparation method of antitoxin suitable for high pressure conversion |
| CN102198401A (en) * | 2011-04-08 | 2011-09-28 | 东南大学 | Cobalt molybdenum CO sulfur-tolerant shift catalyst by using attapulgite clay as carrier and its preparation method |
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