CN101602642A - A kind of scavenging agent that is used for propylene, ethylene light hydrocarbon materials dearsenification and preparation method thereof - Google Patents
A kind of scavenging agent that is used for propylene, ethylene light hydrocarbon materials dearsenification and preparation method thereof Download PDFInfo
- Publication number
- CN101602642A CN101602642A CNA2009100125364A CN200910012536A CN101602642A CN 101602642 A CN101602642 A CN 101602642A CN A2009100125364 A CNA2009100125364 A CN A2009100125364A CN 200910012536 A CN200910012536 A CN 200910012536A CN 101602642 A CN101602642 A CN 101602642A
- Authority
- CN
- China
- Prior art keywords
- solution
- dearsenification
- propylene
- nitrate
- scavenging agent
- 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
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of propylene, ethylene light hydrocarbon materials dearsenification scavenging agent of being used for is to be carrier with the aluminum oxide, and cupric oxide is an active ingredient, zinc oxide is propylene, the ethylene feed dearsenification scavenging agent of auxiliary agent, contain by weight percentage that CuO is 32-35%, ZnO is 33-40%, and surplus is an aluminum oxide.Dearsenification scavenging agent of the present invention is without any need for pre-treatment, can be directly used in the production technique of propylene, ethylene light hydrocarbon materials dearsenification of high-speed, high hydrogen arsenide concentration.This scavenging agent can be 1200-2100hr-1 in normal temperature, normal pressure, air speed, is equivalent to liquid air speed for using under the condition of 4.5-8.0hr-1, has dearsenification precision height, arsenic characteristics capacious.Can at normal temperatures and pressures arsenic content in the raw material be removed to below the 5ppb from 1000ppm, saturated arsenic capacity reaches more than 30%, and industry effectively arsenic is held greater than 15%.And has stronger desulfurizing function.
Description
Technical field
The present invention relates to a kind of scavenging agent, what be specifically related to is a kind of scavenging agent that is used for material dearsenifications such as propylene, ethene.
Background technology
The dearsenic agent of light hydrocarbon materials such as propylene, ethene has crucial application in petrochemical complex is produced.In recent years, along with constantly carrying out of Oil extraction, arsenic content was the trend that rises year by year in the oil product.Daqing oil and Xinjiang Oil Regions all belong to high arsenic crude oil in the crude oil in China, and especially Daqing oil arsenic content it is said that the world is the highest.The product of high arsenic butter product secondary processing gained often requires the arsenic content can not be too high as the polymerizing catalyst of materials such as propylene, ethene or other deep processing catalyzer, otherwise can cause these poisoning of catalyst, causes polyreaction to carry out.
In the industrial production in the processing requirement propylene of propylene polymerization arsenic content can not be higher than 20ppb, otherwise can cause polyreaction normally not carry out, the polymerization degree is lower, so polymerization-grade propylene generally controls arsenic content below 10ppb, even lower.Arsenic content height in the propylene is directly related with the source of propylene.At present, arsenic content is up to 200ppb even 10000ppb in the domestic polypropylene producer raw material that has, and these producers have run into the dearsenification problem that presses for solution.The existence of the arsenide overwhelming majority in the propylene is a hydrogen arsenide, thus the dearsenification problem of propylene actual be the problem that removes of hydrogen arsenide.
In order to solve the problem that runs in the industrial production, the polypropylene factory that has has now adopted the dearsenic agent of the catalyzer of petroleum naphtha dearsenification as propylene feedstocks, these catalyzer were not to develop for the propylene dearsenification specially originally, but used the product in other field.These products exist shortcomings such as the arsenic capacity is little, and porosity is little, and the effective rate of utilization of active ingredient is also very low, and bulk density is big, and the one-time pad expense is higher.
Summary of the invention
A kind of scavenging agent that is used for propylene, ethylene light hydrocarbon materials dearsenification that the objective of the invention is to provide in order to solve the above-mentioned problems in the prior art.
Another object of the present invention provides a kind of preparation method who is used for propylene, ethylene light hydrocarbon materials dearsenification scavenging agent.
The technical scheme that adopts is:
A kind of scavenging agent that is used for propylene, ethylene light hydrocarbon materials dearsenification is to be carrier with the aluminum oxide, and cupric oxide is an active ingredient, zinc oxide is propylene, the ethylene feed dearsenification scavenging agent of auxiliary agent, contain by weight percentage that CuO is 32-35%, ZnO is 33-40%, and surplus is an aluminum oxide.
A kind of preparation method who is used for propylene, ethylene light hydrocarbon materials dearsenification scavenging agent comprises following processing step:
1, batching
Raw material comprises mantoquita, zinc salt and the aluminium salt of solubility, can adopt the nitrate or the vitriol of solubility.Alkaline condition can adopt yellow soda ash, sodium bicarbonate, aqueous sodium hydroxide solution or ammoniacal liquor.
2, the mantoquita with 390-400kg adds water to 1000L, and it is standby to make copper salt solution;
The zinc salt of 500-510kg is added water to 1000L, and it is standby to make zinc salt solution;
900-910kg aluminium salt is added water to 1000L.
3, get and contain Na
2(weight percent) alkaline aqueous solution of O 6-12% is placed in the reactor, under agitation with in the copper salt solution and the above-mentioned zinc salt for preparing and aluminum saline solution and stream inflow reactor that prepare, under 20-70 ℃ of condition, heat coprecipitation reaction, flow velocity is 7.5 for suitable with solution and reactor neutral and alkali solution contact position pH value, when the pH value of full still solution is 7.5, continue to stir precipitation 1-2 hour, after-filtration, washing, filter cake is following dry 24 hours in 100-120 ℃, again at 300-380 ℃ of following roasting 4-5 hour, carry out compressing tablet or extrusion again and reach required shape and specification, get product.
Above-mentioned alkaline aqueous solution is to be made into by yellow soda ash, sodium bicarbonate or sodium hydroxide to contain Na
2O is the aqueous solution of 6-12%.
The optional cupric nitrate of above-mentioned mantoquita, the optional zinc nitrate of zinc salt, the optional aluminum nitrate of aluminium salt.
Advantage of the present invention:
Dearsenification scavenging agent of the present invention is without any need for pre-treatment, can be directly used in the production technique of propylene, ethylene light hydrocarbon materials dearsenification of high-speed, high hydrogen arsenide concentration.This scavenging agent can be 1200-2100hr-1 in normal temperature, normal pressure, air speed, is equivalent to liquid air speed for using under the condition of 4.5-8.0hr-1, has dearsenification precision height, arsenic characteristics capacious.Can at normal temperatures and pressures arsenic content in the raw material be removed to below the 5ppb from 1000ppm, saturated arsenic capacity reaches more than 30%, and industry effectively arsenic is held greater than 15%.And has stronger desulfurizing function.
Dearsenic agent of the present invention adopts the method for salt co-precipitation under alkaline condition of solubility to be prepared from, and is a kind of environmentally friendly dearsenic agent.
Embodiment
Embodiment one
A kind of preparation method who is used for the scavenging agent of propylene, ethylene light hydrocarbon materials dearsenification is:
The cupric nitrate of 390-400Kg is added water to 1000L, and it is standby to make copper nitrate aqueous solution;
The 500-510kg zinc nitrate is added water to 1000L, and it is standby to make zinc nitrate aqueous solution;
The 900-910Kg aluminum nitrate is added water to 1000L, and it is standby to make aluminum nitrate aqueous solution;
Yellow soda ash, sodium hydroxide or sodium bicarbonate are mixed with Na
2O content is that the aqueous solution of 6-12% is standby;
With the above-mentioned yellow soda ash for preparing, sodium hydroxide or sodium hydrogen carbonate solution join in the reactor earlier, under whipped state with the cupric nitrate for preparing, zinc nitrate and aluminum nitrate solution and stream join in the basic solution in the reactor coprecipitation reaction under 20-70 ℃ of heating condition, flow velocity is 7.5 for suitable with solution and reactor neutral and alkali solution contact position pH value, when the pH value of complete soln in the still is 7.5, continue to stir precipitation 1-2 hour, after-filtration, washing, filter cake is following dry 24 hours in 100-120 ℃, again at 300-380 ℃ of following roasting 4-5 hour, carry out compressing tablet or extrusion again and reach required shape and specification and get product.
Embodiment two
A kind of preparation method who is used for the scavenging agent of propylene, ethylene light hydrocarbon materials dearsenification is:
394g cupric nitrate, 504g zinc nitrate, 896g aluminum nitrate are mixed with the 1000ml aqueous solution respectively, 1000g yellow soda ash is mixed with 1000ml solution, sodium carbonate solution is put into reactor, under whipped state, be heated to 60 ℃, cupric nitrate, zinc nitrate and aluminum nitrate solution and stream are added in the sodium carbonate solution, flow velocity is 50ml/hr (being that point of contact place pH value is 7.5), co-precipitation 1.5 hours, again after filtration, washing is back following dry 24 hours in 100 ℃, be extruded into ∮ 1.5X3-5mm strip after 4 hours in 350 ℃ of following roastings again, get product.
Embodiment three
A kind of preparation method who is used for the scavenging agent of propylene, ethylene light hydrocarbon materials dearsenification is:
Copper sulfate, zinc sulfate is mixed with respectively to contain CuO, ZnO be 13% the aqueous solution, aluminum nitrate is mixed with Al
2O
3Content is 10% the aqueous solution, with 1000ml1: 6 ammoniacal liquor are put into reactor, under airtight whipped state, be heated to 30 ℃, cupric nitrate, zinc nitrate and aluminum nitrate solution and stream are added in this ammonia soln, guarantee that liquid stream point of contact place pH value is 7.5, when the complete soln pH value is 7.5 in the still, co-precipitation finishes, again after filtration, washing back in 100 ℃ dry 24 hours down, be extruded into ∮ 1.5X3-5mm strip after 4 hours in 380 ℃ of following roastings again, get product.
Dearsenification effect test example of the present invention:
1, does the initial activity test on the miniature evaluating apparatus of dearsenic agent 10ml with example 2 and 3.Test condition is that normal temperature, normal pressure, air speed are 1200-1600hr
-1, the dearsenic agent loading amount is 5ml, raw material is the propylene of 1543ppb for arsenic content.Test result is listed in the table below.
As can be seen from the above table, dearsenic agent of the present invention is at air speed 1200-2100hr
-1, arsenic content is always less than 3ppb in the reactor outlet material under the normal temperature, normal pressure, arsenic-removing rate illustrates that greater than 99% this dearsenic agent has excellent dearsenification activity.
2, the dearsenic agent that will do initial activity test is done the test of arsenic capacity under normal temperature, normal pressure.The results are shown in following table
In the experiment of test dearsenic agent arsenic capacity, when arsenic content is greater than 1000ppb in the outlet, draw off sample, the arsenic capacity that records sample example 1 is 30.33%, the arsenic capacity of example 2 is 31.68%, this shows, the saturated arsenic of this dearsenic agent holds greater than 30%, and the dearsenification precision is higher, can be that the raw material of 1000ppm is removed to less than below the 5ppb with arsenic content.
Claims (5)
1, a kind of propylene, ethylene light hydrocarbon materials dearsenification scavenging agent of being used for is characterized in that with the aluminum oxide being carrier, and cupric oxide is an active ingredient, zinc oxide is propylene, the ethylene feed dearsenification scavenging agent of auxiliary agent, contain by weight percentage that CuO is 32-35%, ZnO is 33-40%, and surplus is an aluminum oxide.
2, a kind of preparation method who is used for propylene, ethylene light hydrocarbon materials dearsenification scavenging agent according to claim 1 is characterized in that comprising following processing step:
1) batching
Raw material comprises mantoquita, zinc salt and the aluminium salt of solubility, and alkaline condition can adopt yellow soda ash, sodium bicarbonate, aqueous sodium hydroxide solution or ammoniacal liquor;
2) mantoquita with 390-400kg adds water to 1000L, and it is standby to make copper salt solution;
The zinc salt of 500-510kg is added water to 1000L, and it is standby to make zinc salt solution;
900-910kg aluminium salt is added water to 1000L, and it is standby to make aluminum saline solution;
3) get and contain Na
2O is placed in the reactor for the alkaline aqueous solution of 6-12% or ammoniacal liquor by weight percentage, under agitation with in the copper salt solution and the above-mentioned zinc salt for preparing and aluminum saline solution and stream inflow reactor that prepare, under 20-70 ℃ of condition, heat coprecipitation reaction, flow velocity is 7.5 for suitable with solution and reactor neutral and alkali solution contact position pH value, when the pH value of full still solution is 7.5, continue to stir precipitation 1-2 hour, filter, washing, filter cake is following dry 24 hours in 100-120 ℃, again at 300-380 ℃ of following roasting 4-5 hour, carry out compressing tablet or extrusion again and reach required shape and specification and be finished product; The alkali of preparation alkaline aqueous solution is yellow soda ash, sodium bicarbonate, sodium hydroxide or ammoniacal liquor.
3, a kind of preparation method who is used for propylene, ethylene light hydrocarbon materials dearsenification scavenging agent according to claim 2 is characterized in that:
The cupric nitrate of 390-400Kg is added water to copper nitrate aqueous solution, 500-510kg zinc nitrate that 1000L makes to be added water to zinc nitrate aqueous solution that 1000L makes and 900-910Kg aluminum nitrate and adds water to aluminum nitrate aqueous solution that 1000L makes and stream and flow in the above-mentioned reactor that basic solution is housed.
4, a kind of preparation method who is used for propylene, ethylene light hydrocarbon materials dearsenification scavenging agent according to claim 2 is characterized in that:
394g cupric nitrate, 504g zinc nitrate, 896g aluminum nitrate are mixed with the 1000ml aqueous solution respectively, 1000g yellow soda ash is mixed with 1000ml solution, sodium carbonate solution is put into reactor, under whipped state, be heated to 60 ℃, cupric nitrate, zinc nitrate and aluminum nitrate solution and stream are added in the sodium carbonate solution, flow velocity is 50ml/hr, co-precipitation 1.5 hours, again after filtration, washing is back following dry 24 hours in 100 ℃, be extruded into ∮ 1.5X3-5mm strip after 4 hours in 350 ℃ of following roastings again, be finished product.
5, a kind of preparation method who is used for propylene, ethylene light hydrocarbon materials dearsenification scavenging agent according to claim 2 is characterized in that:
Copper sulfate, zinc sulfate is mixed with respectively to contain CuO, ZnO be 13% the aqueous solution, aluminum nitrate is mixed with Al
2O
3Content is that 10% the aqueous solution is standby; With 1000ml1: 6 ammoniacal liquor are put into reactor, under airtight whipped state, be heated to 30 ℃, the above-mentioned cupric nitrate for preparing, zinc nitrate and aluminum nitrate solution and stream are added in this ammonia soln, guarantee that liquid stream point of contact place pH value is 7.5, when the complete soln pH value was 7.5 in the still, co-precipitation finished, more after filtration, the washing back in 100 ℃ dry 24 hours down, be extruded into ∮ 1.5X3-5mm strip after 4 hours in 380 ℃ of following roastings again, be finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100125364A CN101602642A (en) | 2009-07-15 | 2009-07-15 | A kind of scavenging agent that is used for propylene, ethylene light hydrocarbon materials dearsenification and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100125364A CN101602642A (en) | 2009-07-15 | 2009-07-15 | A kind of scavenging agent that is used for propylene, ethylene light hydrocarbon materials dearsenification and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101602642A true CN101602642A (en) | 2009-12-16 |
Family
ID=41468562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100125364A Pending CN101602642A (en) | 2009-07-15 | 2009-07-15 | A kind of scavenging agent that is used for propylene, ethylene light hydrocarbon materials dearsenification and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101602642A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921426A (en) * | 2012-11-05 | 2013-02-13 | 中国科学院过程工程研究所 | Catalyst for catalytic conversion of biological cellulose and preparation method and applications of catalyst |
| CN103638914A (en) * | 2013-11-19 | 2014-03-19 | 苏州丹百利电子材料有限公司 | Method for regenerating dry harmful mediator |
| CN110639466A (en) * | 2019-09-30 | 2020-01-03 | 四川润和催化新材料股份有限公司 | Dearsenic adsorbent and preparation method thereof |
| CN111036220A (en) * | 2019-12-31 | 2020-04-21 | 沈阳三聚凯特催化剂有限公司 | Dearsenic agent and preparation method thereof |
| CN113999085A (en) * | 2021-12-02 | 2022-02-01 | 西安元创化工科技股份有限公司 | Hydrocarbon raw material deep purification method |
-
2009
- 2009-07-15 CN CNA2009100125364A patent/CN101602642A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921426A (en) * | 2012-11-05 | 2013-02-13 | 中国科学院过程工程研究所 | Catalyst for catalytic conversion of biological cellulose and preparation method and applications of catalyst |
| CN103638914A (en) * | 2013-11-19 | 2014-03-19 | 苏州丹百利电子材料有限公司 | Method for regenerating dry harmful mediator |
| CN110639466A (en) * | 2019-09-30 | 2020-01-03 | 四川润和催化新材料股份有限公司 | Dearsenic adsorbent and preparation method thereof |
| CN110639466B (en) * | 2019-09-30 | 2020-12-01 | 四川润和催化新材料股份有限公司 | Dearsenic adsorbent and preparation method thereof |
| CN111036220A (en) * | 2019-12-31 | 2020-04-21 | 沈阳三聚凯特催化剂有限公司 | Dearsenic agent and preparation method thereof |
| CN113999085A (en) * | 2021-12-02 | 2022-02-01 | 西安元创化工科技股份有限公司 | Hydrocarbon raw material deep purification method |
| CN113999085B (en) * | 2021-12-02 | 2023-12-22 | 西安元创化工科技股份有限公司 | Deep purification method of hydrocarbon raw material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100398202C (en) | Process for preparing Cu-Zn-Al vapor hydroformylation catalyst and products therefrom | |
| CN100567461C (en) | A kind of nickel series hydrogenating catalyst and preparation method thereof, application | |
| CN101602642A (en) | A kind of scavenging agent that is used for propylene, ethylene light hydrocarbon materials dearsenification and preparation method thereof | |
| CN102316983B (en) | Copper-based catalyst manufacturing method, copper-based catalyst, and pretreatment method for same | |
| CN101970105B (en) | Preparation of desulphurisation materials | |
| CN106466611B (en) | Ferrum-based catalyst, preparation method and application prepared by co-precipitation-fusion method | |
| CN102989452B (en) | C2 front-end hydrogenation catalyst containing composite carrier and preparation method | |
| CN106607037B (en) | GTO catalyst for fluid bed and preparation method thereof | |
| CN101690893A (en) | Carbonyl sulfide hydrolysis and preparation method thereof | |
| CN112724048A (en) | Preparation method and application of sulfonate | |
| CN103406119A (en) | Bio-diesel catalyst Ca-Mg-Zn-Al-O and preparation method thereof | |
| CN100534894C (en) | Processes and apparatus for gas production by methanol | |
| CN101284245A (en) | Reaction for preparing hydroxyacetone by selectively dewatering natural glycerol and catalyst | |
| CN110327907A (en) | A kind of efficient regenerating anthraquinone degradation products catalyst and preparation method thereof | |
| CN101455966B (en) | Methanol synthesis gas desulfurizer and preparation method thereof | |
| CN107570182A (en) | Catalyst for alkane isomerization and preparation method thereof and reaction unit | |
| CN106607051B (en) | The catalyst and preparation method thereof of one step producing light olefins of synthesis gas | |
| CN102179251B (en) | Catalyst for synthesizing methanol by fluidized bed and preparation method thereof | |
| CN106582603B (en) | The preparation and its application of aluminium oxide catalyst for isobutanol dehydration | |
| CN100395023C (en) | Catalyst for synthesizing copper based methanol and preparing method | |
| CN101797509B (en) | Used lubricating oil complete hydrogenation type regenerated catalyst and preparation method and application thereof | |
| CN103933927B (en) | solid desulfurizing agent and preparation method thereof | |
| CN102476056A (en) | Catalyst used in fatty alcohol production with fatty acid methyl ester catalyzed hydrogenation technology, preparation method thereof, and application thereof | |
| AU2013294804A1 (en) | Sorbents | |
| CN103949258B (en) | Methods and applications for slurry bed system synthesis gas catalyst for producing dimethyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20091216 |