CN1035256A - Catalyst for removing hydrogen from Co 2 raw gas used to synthesize urea - Google Patents

Catalyst for removing hydrogen from Co 2 raw gas used to synthesize urea Download PDF

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Publication number
CN1035256A
CN1035256A CN 88100942 CN88100942A CN1035256A CN 1035256 A CN1035256 A CN 1035256A CN 88100942 CN88100942 CN 88100942 CN 88100942 A CN88100942 A CN 88100942A CN 1035256 A CN1035256 A CN 1035256A
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catalyst
hydrogen
temperature
volume
carrier
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CN1015050B (en
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徐贤伦
过中儒
詹肇其
汤爱华
徐红兵
谭淑凤
邓友全
李胜利
安立敦
李春华
崔子军
刘恒宁
马军
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

From urea synthesis CO 2Unstripped gas removes hydrogen in (containing CO), belongs to the H under the specific condition 2-O 2Catalytic reaction, catalyst of the present invention is with Al 2O 3Being carrier, is active constituent with the Pd-Pt bimetallic, also contains one or more auxiliary elements, wherein Pd: Al=1.0 * 10 -5: 1.0～5.0 * 10 -3: 1.0, Pd: Pt=1.0: 1.0～50.0: 1.0, Pd: auxiliary element M=0.3: 1.0～40.0: 1.0 (atomic ratios).The characteristics of this catalyst are the reasonable couplings of Pd and Pt metal.Its advantage is: show good low-temperature catalytic oxidation activity and stability in the presence of 0.10%～0.20% (volume) CO, the utilization rate height of noble metal has reduced total consumption of noble metal, has good heat endurance and regenerability.

Description

Catalyst for removing hydrogen from Co 2 raw gas used to synthesize urea
The present invention system utilizes Production by Catalytic Combustion Process from urea synthesis CO 2Eliminate the catalyst of hydrogen in the unstripped gas, belong to H 2+ O 2Catalytic reaction generates the water metallic catalyst.
Furtherd investigate H on the Pt catalyst from nineteen twenty-two Langmuir 2+ O 2Since the mechanism of reaction, to the fifties, because purifying urea synthesis CO has appearred in industrial needs 2The patent of unstripped gas, Diebold[USP 2,999, and 008] adopt the Pt catalyst under 232 ℃, with CO 2The hydrogen that contains in the unstripped gas (0.82V%), CO(0.02V%) and CH 4(0.01V%) Catalytic Oxygen changes into H respectively 2O, CO 2And CO 2+ H 2O.Afterwards, Gavrilov[U.S.S.R Patent, 198,302] and Sang Sak Mok[Neth, Appl., 7,510,544] and their colleagues successively developed noble metal catalysts such as Pd again.Though the trial of oxide catalyst is also arranged, for example: Cr 2O 3-Fe 2O 3-K 2The O system [Japan.23,151(' 63)], but reaction temperature too high (350～400 ℃), the too low (1200～2400h of gas space velocity -1), there is not practical value; Ochiai Masao etc. [Ger, offen 2,604, and 054] delivered the patent that adopts Ru, Rb, Pd or the compound noble metal catalyst of Pt, the catalytic oxidation temperature of hydrogen is reduced to below 300 ℃.Early eighties, also occurred the Pt-V catalyst (J.P.57,205,310] patent.
Late nineteen seventies, urea industry circle have been accepted the lesson of urea plant explosion accident for several times.CO is adopted in beginning on commercial plant 2Feed gas catalytic dehydrogenation technology, catalyst system therefor type mainly are the CN-101 type Pt/Al of U.S. Engelhard company 2O 3Catalyst.520,000 tons of/year urea plants of several covers that China's the eighties is introduced just have this De-hydrogen Technology.
The CN-101 type catalyst of Engelhard company is Al 2O 3The Pt catalyst that supports, the loading of its Pt are 0.3%(weight), to the requirement of unstrpped gas be: CO 2～91%(volume), H 2～0.93%(volume), O 2The 1.44%(volume), CO＜0.20%(volume), CH 4The 0.06%(volume), CH 3OH≤300ppm, total sulfur content S≤2mg/Nm 3, its suitable operating condition is: reaction pressure (1.43～1.50) * 10 7Pa, inlet reaction temperature, 180～220 ℃, gas space velocity 25000h -1(volume) it is said that this catalyst reaction (～regeneration) cycle is 1 year, useful life 4 years.520,000 tons of/year urea plants of certain general petrochemicals factory once used CN-101 type catalyst to turn round 7300 hours continuously, the reactor inlet temperature long term maintenance is about 220 ℃, can keep the residual hydrogen amount of tail gas below 50ppm, it represents the leading level in the world of late nineteen seventies early eighties.
The objective of the invention is: seek a kind of from urea synthesis CO 2Remove the catalyst of hydrogen in the unstripped gas.It is except at 0.1～0.2%(volume) still have better low temperature activity and the stability in the presence of the CO, also require its noble metal dosage the least possible, and have good heat endurance and satisfy the sulfur poisoning-resistant ability of industrial actual needs.
Detailed description of the present invention:
The present invention is with spherical Al 2O 3Be carrier, its active constituent can also contain at least a other elements as auxiliary agent except that the palladium and platinum of metallic state, and these elements are Na, K, Mg, Ca, Ba, Fe, Co, Ni, Cu, Cr, V etc.
Catalyst carrier can be from aluminium colloidal sol, ball-aluminium oxide, silica-alumina ball or 5A molecular sieve etc.Pd and Pt can be from different salts or metals, as, H 2PdCl 4, H 2PtCl 66H 2O, PdCl 2, PtCl 4, Pd and Pt etc.
A spot of auxiliary element, to the heat endurance that improves catalyst, the anti-poisoning (as sulfur-containing compound, CO, CH 3Poisonous substances such as OH) ability has positive effect, and generally with its oxide, the form of composite oxides or corresponding salt occurs auxiliary element in catalyst.
The carrier of above-mentioned catalyst, active constituent has certain proportionate relationship between the auxiliary element:
The atomic ratio of Pd and Al can be 1.0 * 10 -5: 1.0～5.0 * 10 -3: 1.0, atomic ratio is 1.0 * 10 preferably -4: 1.0～1.0 * 10 -3: 1.0, the atomic ratio of Pd and Pt can be 1.0: 1.0～50.0: 1.0, atomic ratio is 1.0: 1.0～20.0: 1.0 preferably, and the atomic ratio of Pd and auxiliary element M can be 0.3: 1.0～40.0: 1.0, and atomic ratio is 1.0: 1.0～10.0: 1.0 preferably.
The Preparation of catalysts method can be with infusion process (soak altogether or divide and soak), ion-exchange, spray drying process etc.
The Preparation of catalysts process is: with the Al that chooses 2O 3Carrier (specific area 140～180m 2/ g, φ 2.5～3.2mm) oven dry, metal or salt dissolving with selected Pd, Pt are mixed with the solution that concentration is 0.03～0.09 mole/liter.Give preparing solution earlier or directly its esters being added above-mentioned active constituent solution according to the chemical property of selecting auxiliary agent for use and dissolve it.
During dipping, the volume ratio that the solution for preparing suitably is diluted to solution and carrier is close to 1: 1, is uniformly impregnated within Al under room temperature 2O 3On the carrier, and stir rapidly, left standstill 0.5～1 hour.Then in 80～120 ℃ of dryings 3～8 hours, and be interrupted and stir, till oven dry (catalyst weightening finish≤5%), usually this moment, the catalyst outward appearance be the light gray or the color of auxiliary agent ion slightly, roasting at high temperature subsequently, its temperature can be in 350～700 ℃ of scopes, temperature is 450～600 ℃ preferably, then through hydrogen reducing, its reduction temperature can be 230 ℃～600 ℃, temperature is 250 ℃～500 ℃ preferably, and used hydrogen can be pure hydrogen or hydrogen-nitrogen mixed gas, and its hydrogen gas space velocity is 300-1000 hour -1(volume), the gained finished catalyst is generally light gray or Dark grey.
With the described catalyst of present disclosure, consist of H at unstripped gas 20.5～1.2%; O 20.5～1.2%; CO 0.1～0.2%; N 22～5%; CO 293～96%(volume %), on atmospheric fixed bed reactor, the residual hydrogen amount that makes reaction end gas less than the required minimum response temperature of 10ppm (minimum " the full conversion " temperature, TLTC) usually at 100～140 ℃, its hydrogen conversion 〉=99.9%.
Consist of with catalyst of the present invention used raw material of industry in urea production: CO 296～98%; H 20.90～1.0%; O 21.3～1.4%; CO≤0.2%, (volume %); CH 3OH≤300ppm, total sulfur content S≤2.0mg/Nm 3, reaction pressure is (1.32～1.47) * 10 7Pa, the gas volume air speed is (2.8～3.2) * 10 4Hour -1, reactor inlet temperature is under 170～210 ℃ the situation, can make dehydrogenation after the residual hydrogen amount of tail gas less than 50ppm, fundamentally solve the explosion-proof problem of urea plant 1 year reaction time, guaranteed safety in production.Reduce the emptying amount of ammonia, improved economic benefit.
Compared with the prior art the substantive distinguishing features that has of the present invention
The outstanding feature of catalyst of the present invention is: the bimetallic reasonable coupling of (1) Pd-Pt makes it show the good low-temperature dehydrogenation activity in the presence of CO; (2) utilize active constituent ion, auxiliary element ion, H 3O +Ion and acid ion are at carrier A l 2O 3On competitive Adsorption mechanism, active constituent is formed on carrier reasonably distributes, reduced noble metal dosage, improved the effective rate of utilization of noble metal; (3) add suitable adjuvants, improved the heat endurance of catalyst.
Implementation of the present invention and most preferred embodiment
Example 1. is got the Al that Wenzhou chemical factory produces 2O 3Ball (φ 2.5～φ 3.2mm), through 110～130 ℃ of down oven dry, it is standby to take by weighing 20.00g.Measure the H that concentration is 0.0059g Pt/ml 2PtCl 6Solution 1.70ml is diluted to 20ml, pours the Al that weighs up into 2O 3Ball floods it, left standstill after stirring 30 minutes, and 110～120 ℃ of oven dry down in baking oven, and be interrupted and stir.Place muffle furnace in 500 ℃ of following roastings 3 hours, reduce to room temperature naturally.Measure the H that concentration is 0.0094g Pd/ml 2PdCl 4Solution 2.12ml adds CH 3COOK0.085 gram is diluted to 20ml, pour into the above-mentioned sample that is chilled to nearly room temperature flood it, after leaving standstill, drying, in 500 ℃ of following roastings 3 hours, at hydrogen stream (H 2Volume space velocity 300～500h -1) in 500 ℃ of following reductase 12s hour, be chilled to room temperature naturally, take out finished catalyst and be light gray uniformly.
Consist of H at unstripped gas 21.0～1.2%; O 21.0～1.2%; CO0.14%; CO 290～95%; N 23.0～6.0(volume %).The gas volume air speed is (2.7 ± 0.2) * 10 4h -1Situation under, reach that the required minimum response temperature of residual hydrogen amount＜10ppm is 139 ℃ in the tail gas.
In example 2. examples 1 with 1.70ml H 2PdCl 6Solution and 2.12ml H 2PdCl 4Solution mixes, and adds CH 3COOK 0.085 gram also is diluted to 20ml, dipping 20.00g Al 2O 3, through leave standstill, drying, 500 ℃ of roastings, 500 ℃ of reduction, finished catalyst, raw materials used gas and volume space velocity thereof in the use-case 1, the minimum response temperature that makes residual hydrogen be lower than 10ppm is 132 ℃.
Example 3. adopts the catalyst of examples 2, allocates 2～5mg/Nm again in the used unstripped gas in example 1 3H 2S is (2.7 ± 0.2) * 10 in the feed gas volume air speed 4Hour -1Situation under carry out stability test, its residual hydrogen amount is as shown in table 1 less than the variation of 10ppm desired reaction temperature.
Table 1. minimum " the full conversion " temperature is with the variation in reaction time
TLTC(℃ of reaction time (h)) TLTC(℃ of reaction time (h))
200 150 2000 172
400 150 2200 170
600 155 2400 174
800 158 2600 176
1000 162 2800 172
1200 168 3000 174
1400 168 3200 176
1600 172 3400 176
1800 168
Example 4. is measured the H that 1.70ml concentration is 0.0059g Pt/ml 2PtCl 6Solution, with 4.24ml concentration be the H of 0.0094g Pd/ml 2PdCl 4Solution mixes, and adds CH 3The COONa0.095 gram, and be diluted to 20ml, dipping 20.00g Al 2O 3Ball, drying, 500 ℃ of roasting 3h, 500 ℃ of reductase 12 h, the unstripped gas of gained finished catalyst use-case 1 is (2.7 ± 0.2) * 10 in the unstripped gas air speed 4h -1Situation under, reaching the reaction temperature that residual hydrogen is lower than 10ppm is 128 ℃.
Example 5. usefulness 5A molecular sieves replace the carrier of example 4 catalyst, and other preparation conditions and reaction condition be with example 4, the residual hydrogen amount reaction temperature that is lower than 10ppm is 132 ℃.
Example 6. is measured the H that 1.70ml concentration is 0.0059gPt/ml 2PtCl 6Solution and 6.36ml concentration are the H of 0.0094gPd/ml 2PdCl 4Solution mixes, and adds KHCO 30.15 gram, and be diluted to 20ml, be immersed in 20.00g Al 2O 3On the ball, through leave standstill, drying, 500 ℃ of roasting 3h, 500 ℃ of reductase 12 h, the unstripped gas of gained catalyst use-case 1 and (2.7 ± 0.2) * 10 4h -1Air speed, residual hydrogen be 124 ℃ less than the 10ppm reaction temperature.
Example 7. is measured the H that 6.36ml concentration is 0.0094gPd/ml 2PdCl 4Solution adds CH 3The COOK0.14 gram is diluted to 20ml, is immersed in 20.00g Al 2O 3On the ball, through leave standstill, drying, 500 ℃ of roastings, 500 ℃ of reduction, finished catalyst, the unstripped gas of use-case 1 and gas space velocity, residual hydrogen is 138 ℃ less than the reaction temperature of 10ppm.
Example 8. usefulness 10.20ml concentration are the H of 0.0059gPt/ml 2PtCL 6Solution replaces the H in the example 7 2PdCl 4Solution, other preparations and reaction condition is with example 7, must residual hydrogen be 154 ℃ less than the reaction temperature of 10ppm.
Through 500 ℃ of baked semi-finished product, be dissolved with 0.31 gram Cr(NO in example 9. examples 4 with 20ml 3) 39H 2The aqueous solution of O floods it, again through leave standstill, drying, 500 ℃ of roastings 3 hours, 500 ℃ of reductase 12 h, the unstripped gas and the gas space velocity of gained catalyst use-case 1, residual hydrogen is 128 ℃ less than the reaction temperature of 10ppm.
Example 10. is measured the H that 8.50ml concentration is 0.0094gPd/ml 2PdCl 4Solution and 3.40ml concentration are the H of 0.0059gPt/ml 2PtCl 6Solution mixes, and adds 0.015gK 2S to 20ml, impregnated in 20.00g Al with distilled water diluting 2O 3On the ball, through leave standstill, dry, 500 ℃ of roasting 3h, 500 ℃ of reductase 12 h, gained finished catalyst use-case 1 raw materials used gas and reaction condition, it is 94 ℃ that residual hydrogen is lower than the 10ppm desired reaction temperature.
Most preferred embodiment is an example 3.

Claims (4)

1, a kind of from urea synthesis CO 2Remove the catalyst of hydrogen in the unstripped gas with Production by Catalytic Combustion Process, the activity of such catalysts component is Pd and Pt, also contains following one or more auxiliary elements, and Na, K, Mg, Ca, Ba, Fe, Co, Ni, Cu, Cr, V etc. select AL for use 2O 3, or contain Al 2O 3Silica one aluminium oxide, molecular sieve etc. be carrier, it is characterized in that: following relationship is arranged, Pd between active constituent, auxiliary element and the carrier: Al=1.0 * 10 -5: 1.0～5.0 * 10 -3: 1 (atomic ratio), Pd: Pt=1.0: 1.0～50.0: 1.0 (atomic ratios), Pd: auxiliary element M=0.3: 1.0～40.0: 1.0 (atomic ratios).
2, as claims 1 described catalyst, it is characterized in that, between Pd and the Al preferably atomic ratio be 1.0 * 10 -4: 1.0～1.0 * 10 -3: 1.0.
3, catalyst as claimed in claim 1 is characterized in that: between Pd and the Pt preferably atomic ratio be 1.0: 1.0～20.0: 1.0.
4, catalyst as claimed in claim 1 is characterized in that: preferable atomic ratio is 1.0: 1.0～10.0: 1.0 between Pd and the auxiliary element M.
CN 88100942 1988-02-23 1988-02-23 Catalyst for removing hydrogen from co2 raw gas used to synthesize urea Expired CN1015050B (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1088399C (en) * 1998-02-25 2002-07-31 中国科学院大连化学物理研究所 Anti-toxic catalyst for deoxidation in high concentration CD and its preparation
CN1088622C (en) * 1998-11-26 2002-08-07 北京大学 Palladium catalyst with carrier of titanium oxide-alumina compound, and its preparing process and application
CN1089631C (en) * 1999-10-26 2002-08-28 湖北省化学研究所 Dehydrogenation catalyst for urea synthesizing CO2 gas and its preparation
CN100368280C (en) * 2002-12-20 2008-02-13 本田技研工业株式会社 Alkali-containing catalyst formulations for low and medium temperature hydrogen generation
CN101380574B (en) * 2007-09-06 2010-11-24 中国科学院生态环境研究中心 Catalyst for complete oxidation of formaldehyde at room temperature
CN104117353A (en) * 2014-08-12 2014-10-29 西安凯立化工有限公司 Catalyst for preparing o-fluoroaniline from o-fluoronitrobenzene by hydrogenation and preparation method of catalyst
CN109529830A (en) * 2018-12-18 2019-03-29 沈阳化工大学 A kind of dimethyl sulfide carbon monoxide-olefin polymeric preparation method

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1088399C (en) * 1998-02-25 2002-07-31 中国科学院大连化学物理研究所 Anti-toxic catalyst for deoxidation in high concentration CD and its preparation
CN1088622C (en) * 1998-11-26 2002-08-07 北京大学 Palladium catalyst with carrier of titanium oxide-alumina compound, and its preparing process and application
CN1089631C (en) * 1999-10-26 2002-08-28 湖北省化学研究所 Dehydrogenation catalyst for urea synthesizing CO2 gas and its preparation
CN100368280C (en) * 2002-12-20 2008-02-13 本田技研工业株式会社 Alkali-containing catalyst formulations for low and medium temperature hydrogen generation
CN101380574B (en) * 2007-09-06 2010-11-24 中国科学院生态环境研究中心 Catalyst for complete oxidation of formaldehyde at room temperature
CN104117353A (en) * 2014-08-12 2014-10-29 西安凯立化工有限公司 Catalyst for preparing o-fluoroaniline from o-fluoronitrobenzene by hydrogenation and preparation method of catalyst
CN104117353B (en) * 2014-08-12 2016-04-13 西安凯立新材料股份有限公司 A kind of o-fluoronitrobenzene Hydrogenation is for the catalyst of adjacent fluoroaniline and preparation method
CN109529830A (en) * 2018-12-18 2019-03-29 沈阳化工大学 A kind of dimethyl sulfide carbon monoxide-olefin polymeric preparation method

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