CN1044599C - Method for removing trace impurity carbon monoxide in gas mixture - Google Patents
Method for removing trace impurity carbon monoxide in gas mixture Download PDFInfo
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- CN1044599C CN1044599C CN94115415A CN94115415A CN1044599C CN 1044599 C CN1044599 C CN 1044599C CN 94115415 A CN94115415 A CN 94115415A CN 94115415 A CN94115415 A CN 94115415A CN 1044599 C CN1044599 C CN 1044599C
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- solution
- cuo
- alpha
- zno
- olefin
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000012535 impurity Substances 0.000 title claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 title description 2
- 239000000203 mixture Substances 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000004711 α-olefin Substances 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- -1 vitriol Chemical compound 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 12
- 229930195734 saturated hydrocarbon Natural products 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- IIPKBWQWKYOKRA-UHFFFAOYSA-N ethane;prop-1-ene Chemical group CC.CC=C IIPKBWQWKYOKRA-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A process for removing CO from a gas containing trace amounts (< 10ppm) of CO in alpha-olefins and saturated hydrocarbons by contacting the gas with a CuO/ZnO catalyst in which the CO is oxidized to CO2The CO conversion rate can reach about 100%, and the service life of the catalyst is 3-5 years.
Description
The present invention relates to from the gaseous mixture that contains the following CO of 10PPM, remove the method for CO.More particularly, the present invention relates to the alpha-olefin and stable hydrocarbon below containing 10PPM, particularly from C
2-4Alpha-olefin and C
2-4In the stable hydrocarbon, the CO Catalytic Oxygen is changed into CO
2Thereby, the method for from above-mentioned gas mixture, removing CO.
As everyone knows, the CO content in the alpha-olefin is usually below 10PPM.Under this concentration, CO is very sensitive to employed catalyzer in the subsequent reactions.Therefore, require that the content of impurity CO is lower than 0.1PPM in the alpha-olefin.For this reason, people have carried out research work in large quantities, seek a kind of economy and the easy method of removing CO with expectation.
Remove in the prior art that the method for trace amounts of CO has three kinds in the alpha-olefin: first kind is chemical absorption method, CO can be reduced to 0.24PPM, employed absorption liquid costliness in this method, the absorption liquid that alpha-olefin is carried secretly can cause the pollution of lower procedure, the particularly important is this method the content of impurity CO is reduced to below the 0.1PPM.Second kind is absorption method, and this method adopts adsorbents adsorb CO such as gac, only is its Adsorption law of research.The third is a catalysis method, and the alpha-olefin such as the ethene that contain trace amounts of CO are contacted with the solid catalyst of metal oxide, makes CO wherein be oxidized to CO
2, CO is wherein reduced to below the 0.1PPM.This method is simple to operate, and cost is low, and is very attractive to industrializing implementation.The catalyzer that has used in the catalytic oxidation has metal oxide catalysts such as Pd, Ag, Mn, Co, Cu, Ni, Fe and Cr, complicated component, preparation difficulty.
For example, introduced the method for trace impurity CO in a kind of alpha-olefin of removing, particularly ethene or the propylene among the US301493, this method is that ethene or propylene are contacted with cuprous aqueous ammonium, absorb CO wherein, make it to form complex compound, handle this clathrate separation then and go out CO with copper compound.This method complexity, uneconomical.
CN92113063.5 discloses a kind of method of removing CO from alpha-olefin and stable hydrocarbon.This method is under 0-150 ℃, makes alpha-olefin and stable hydrocarbon, particularly C
2-4Alpha-olefin and C
2-4Stable hydrocarbon contacts with following catalyst system, and CO is wherein changed into CO by Catalytic Oxygen
2This catalyst system typically is CuCr
2O
4, processed material air speed is 2.3-8hr
-1Use deleterious chromic salts in the preparation catalyzer process, contaminate environment does not have the prospect of industrial application.
The inventor has proposed to use the catalyst system of the mixed oxide of CuO/ZnO through study for many years meticulously, removes alpha-olefin, particularly C
2-4Alkene and C
2-4(＜10PPM) CO has finished the present invention to trace impurity in the stable hydrocarbon.
Therefore, the purpose of this invention is to provide a kind of alpha-olefin of removing, particularly C
2-4Alkene and C
2-4(＜10PPM) the method for CO of trace impurity in the stable hydrocarbon.
Second purpose of the present invention provides the employed catalyzer of aforesaid method.
The 3rd purpose of the present invention provides above-mentioned Preparation of catalysts method.
According to the present invention, the method for removing trace impurity CO from alpha-olefin and stable hydrocarbon comprises: at 50-150 ℃, under preferred 70-120 ℃ the temperature, reaction pressure is 0.2-2.94MPa, and air speed is 1000-3000hr
-1The time, the alpha-olefin or the stable hydrocarbon that contain CO are contacted with a kind of catalyzer, make CO Catalytic Oxygen wherein change into CO
2This catalyzer is to be active ingredient with CuO, and ZnO is a carrier, and CuO: ZnO=1: 1.5-4.0 is preferably 1: the catalyst system of 1.7-3 (weight ratio).
Employed Preparation of catalysts method is general in the art method for preparing catalyst in the inventive method, all can adopt as pickling process, mixing method and coprecipitation method etc.But preferred coprecipitation method.Concrete preparation process is as follows:
(1) preparation mantoquita and zinc solution are respectively A solution and B solution.Employed mantoquita or zinc salt can be inorganic salt, as carbonate such as Cu (Zn) CO
3Nitrate such as Cu (Zn) (NO
3)
2Vitriol such as Cu (Zn) SO
4Deng, organic acid salt such as acetate, oxalate and Citrate trianion etc., preferably nitrate, acetate.
(2) preparation alkaline solution (C), alkali can be selected from NaOH, KOH, NH
4OH, Na
2CO
3(NH
4)
2CO
3Deng;
(3) neutralization is about to A solution and/or B solution and adds in the C solution, or C solution is added in A solution and/or the B solution, and making its pH value is 5-9, preferred 6.0-7.8;
(4) throw out of gained in the washing step (3), the negatively charged ion in the disgorging and institute's remaining impurities positively charged ion;
(5) throw out of drying step (4) gained, drying temperature is 50-120 ℃, be more than 10 hours time of drying;
(6) roasting
The product that step (5) obtains is inserted roasting in the stove, and maturing temperature is 300-600 ℃, and the time is 2-10 hour;
(7) compression molding
General tackiness agent mixes in CuO/ZnO saccharoid that above-mentioned roasting is good and the present technique field, is pressed into column with tabletting machine.
The rerum natura of catalyzer is:
Granularity φ 3 * 3-φ 5 * 5mm
Specific surface area 10-80m
2/ g is preferably 40-75m
2/ g
Bulk density 1.3-1.8g/ml
Side pressure strength＞8Kg/
The grain fineness number 40-200A of CuO
Below, further describe the present invention with limiting examples, any improvement or modification that those skilled in the art have done by above-mentioned spirit, only otherwise leave spirit of the present invention, all within the scope of the present invention and the claim that proposed.Example 1
The preparation catalyzer
Measure 300ml copper nitrate solution and 300ml zinc nitrate solution, wherein contain cupric nitrate 86.8g, zinc nitrate 213g, be respectively A solution and B solution;
(the NH of preparation 10%
4)
2CO
3Solution, this is a C solution, and A solution and B solution are added in the there-necked flask, and after being heated to certain temperature, dripping the solution C of 600ml, the gained precipitation is after washing, drying, 400 ℃ of roastings 5 hours, use the tabletting machine moulding then, promptly make employed catalyzer in the method for the present invention.Its rerum natura is as follows:
Granularity φ 4 * 4mm
Specific surface area 53.4m
2/ g
Bulk density 1.6g/ml
Side pressure strength 10.5Kg/
The brilliant degree 55A example 2 of CuO
Carry out the test that removes of impurity CO in alpha-olefin and the stable hydrocarbon with example 1 prepared catalyzer.Test is carried out in fixed-bed tube reactor.Test conditions is as follows:
Treat purified gas: ethene, propylene, butene-1, ethane, propane, just-butane
Treat the CO concentration 5PPm in the processed gas
Air speed 2500hr
-1
79 ℃ of temperature of reaction
Reaction pressure 2.0MPa
Test-results such as table 1.
Table 1
| Project name | CO (PPm) before the reaction | Reaction back CO (PPm) |
| Ethene | 5 | ＜0.1 |
| Ethane | ||
| Propylene | 5 | ＜0.1 |
| Propane | ||
| Butene-1 | 5 | ＜0.1 |
| Just-butane |
Example 1 catalyzer is used for ethene purified mould examination evaluation result and sees Table 2
Table 2
| The accumulative total reaction times (hr) | Reaction pressure (MPa) | Temperature of reaction (℃) | CO(PPm) | Transformation efficiency (%) | Air speed (hr -1) | |
| Before the reaction | After the reaction | |||||
| 0.3 | 1.95 | 78 | 1.75 | ＜0.1 | ～100 | 2500 |
| 27 | 2.0 | 83 | 2.65 | ＜0.1 | ～100 | 2500 |
| 63 | 1.96 | 79 | 1.18 | ＜0.1 | ～100 | 2500 |
| 99 | 2.0 | 81 | 0.93 | ＜0.1 | ～100 | 3000 |
| 124 | 2.05 | 86 | 5.22 | ＜0.1 | ～100 | 3000 |
| 148 | 1.97 | 83 | 3.91 | ＜0.1 | ～100 | 3000 |
| 164 | 1.95 | 79 | 0.87 | ＜0.1 | ～100 | 3000 |
| 184 | 2.0 | 84.3 | 1.08 | ＜0.1 | ～100 | 3000 |
| 200 | 2.02 | 84 | 1.38 | ＜0.1 | ～100 | 3000 |
This catalyzer is on probation on the refining test of ethene full scale plant, and the catalyzer loading amount is greater than 6 tons, and 70 ℃-90 ℃ of temperature of reaction can be removed to the CO of＜5PPm＜0.1PPm, and the regeneration period is individual month of 2-7, operational excellence.Example 4
The regeneration test of the catalyzer of example 1
Catalyzer is behind life-time service, and activity reduces gradually, after not reaching processing requirement, must regenerate.The activity of such catalysts of example 1 the results are shown in table 3 with the catalyst activity after the regeneration is compared.
Table 3
| The reaction cumulative time (hr) | New catalysis profit | Catalyzer after the regeneration | ||||
| Temperature of reaction (℃) | CO(PPm) | Temperature of reaction (℃) | CO(PPm) | |||
| Before the reaction | After the reaction | Before the reaction | After the reaction | |||
| 31 63 95 165 254 | 90 90 85 90 100 | 3.76 3.62 6.07 3.76 3.13 | ＜0.1 ＜0.1 ＜0.1 ＜0.1 ＜0.1 | 90 90 90 95 95 | 3.98 3.48 4.16 3.40 4.10 | ＜0.1 ＜0.1 ＜0.1 ＜0.1 ＜0.1 |
Claims (6)
1, a kind of method of removing trace impurity CO from alpha-olefin and stable hydrocarbon comprises: under 70～120 ℃, reaction pressure is 0.2～2.94Mpa, and air speed is 1000～3000hr
-1The time, make to contain＜processed gas for the treatment of of 10ppmCO contacts with solid CuO/ZnO catalyzer, wherein the weight ratio of CuO and ZnO is 1: 1.5～4.0, and the grain fineness number of CuO is 40～200A, and described solid CuO/ZnO catalyzer is by following coprecipitation method preparation:
(1) preparation mantoquita and zinc solution are respectively A solution and B solution, and employed mantoquita or zinc salt can be selected carbonate, nitrate, vitriol, acetate, oxalate or Citrate trianion,
(2) but preparation alkaline solution C alkali NaOH, KOH, NH
4OH, Na
2CO
3, (NH
4)
2CO
3,
(3) C solution is added in A solution and the B solution, making its pH value is 6.0～7.8,
(4) throw out of gained in the washing step (3), the negatively charged ion in the disgorging and institute's remaining impurities positively charged ion,
(5) throw out of drying step (4) gained, drying temperature is 50～120 ℃, be more than 10 hours time of drying,
(6) roasting
The product that step (5) obtains is inserted roasting in the stove, and maturing temperature is 300～600 ℃, and the time is 2～10 hours,
(7) general tackiness agent mixes moulding in the saccharoid of the CuO/ZnO that above-mentioned roasting is good and the present technique field.
2, by the process of claim 1 wherein that alpha-olefin is an alpha-olefins.
3, by the method for claim 1 or 2, wherein alpha-olefin is ethene, propylene or butene-1.
4, by the process of claim 1 wherein that stable hydrocarbon is ethane, propane or just-butane.
5, by the process of claim 1 wherein that the weight ratio of CuO and ZnO is 1: 1.7～3.0.
6, by the process of claim 1 wherein that refining reaction carries out under 70～90 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94115415A CN1044599C (en) | 1994-08-31 | 1994-08-31 | Method for removing trace impurity carbon monoxide in gas mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94115415A CN1044599C (en) | 1994-08-31 | 1994-08-31 | Method for removing trace impurity carbon monoxide in gas mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1117956A CN1117956A (en) | 1996-03-06 |
| CN1044599C true CN1044599C (en) | 1999-08-11 |
Family
ID=5037475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94115415A Expired - Lifetime CN1044599C (en) | 1994-08-31 | 1994-08-31 | Method for removing trace impurity carbon monoxide in gas mixture |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1044599C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478005B (en) * | 2014-09-16 | 2018-08-17 | 中国石油化工股份有限公司 | A method of removing trace amounts of CO |
| CN105879656B (en) * | 2015-11-24 | 2020-01-07 | 上海超硅半导体有限公司 | Solid phase treatment technology for tail gas generated in growth of monocrystalline silicon |
| CN110292929A (en) * | 2018-03-22 | 2019-10-01 | 中国科学院大连化学物理研究所 | CO selective oxidation removal catalyst and its preparation and application in a kind of recycled offgas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3549719A (en) * | 1968-06-17 | 1970-12-22 | Stamicarbon | Process for the purification of olefines |
| US4593148A (en) * | 1985-03-25 | 1986-06-03 | Phillips Petroleum Company | Process for removal of arsine impurities from gases containing arsine and hydrogen sulfide |
| CN1072673A (en) * | 1991-10-08 | 1993-06-02 | 希蒙特公司 | From alpha-olefin and stable hydrocarbon, remove the method for carbon monoxide |
-
1994
- 1994-08-31 CN CN94115415A patent/CN1044599C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3549719A (en) * | 1968-06-17 | 1970-12-22 | Stamicarbon | Process for the purification of olefines |
| US4593148A (en) * | 1985-03-25 | 1986-06-03 | Phillips Petroleum Company | Process for removal of arsine impurities from gases containing arsine and hydrogen sulfide |
| CN1072673A (en) * | 1991-10-08 | 1993-06-02 | 希蒙特公司 | From alpha-olefin and stable hydrocarbon, remove the method for carbon monoxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1117956A (en) | 1996-03-06 |
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Expiration termination date: 20140831 Granted publication date: 19990811 |