CN100384966C - Liquid state petroleum hydrocarbon normal temperature dearsenicating agent and preparation method thereof - Google Patents
Liquid state petroleum hydrocarbon normal temperature dearsenicating agent and preparation method thereof Download PDFInfo
- Publication number
- CN100384966C CN100384966C CNB2005100293446A CN200510029344A CN100384966C CN 100384966 C CN100384966 C CN 100384966C CN B2005100293446 A CNB2005100293446 A CN B2005100293446A CN 200510029344 A CN200510029344 A CN 200510029344A CN 100384966 C CN100384966 C CN 100384966C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- agent
- dearsenic agent
- mesoporous molecular
- precursor
- 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.)
- Expired - Fee Related
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a normal temperature arsenic-removing agent of liquid-oil hydrocarbon and preparing method, which consists of 50-99% middle-hole molecular sieve with arsenic-removing component and 1-50% structural moulding auxiliary material, wherein the molecular sieve is silica middle-hole molecular sieve or silicon-aluminium middle-hole molecular sieve with even aperture at 2-50nm and specific area at 100-1000m2/g, which is selected from one or more composition of nitrate or chloride or sulfate or sulfide or oxalic compound with Cu, Fe, Mn, Ni and Si; the former of active component contains 0.01-20% metal in the arsenic-removing agent.
Description
Technical field
The present invention relates to be used for the isolating additive of refining of petroleum, relate in particular to a kind of liquid condition petroleum hydrocarbon arsenic removal catalyst.
Background technology
As everyone knows, petroleum hydrocarbon particularly the arsenide in the liquid condition petroleum hydrocarbon it follow-uply is being processed with significantly negative impact.Distinct issues are the poisonings that cause catalyzer.Arsenide also is deposited on pipe surface easily, and corrosion pipeline causes a hidden trouble.When serious, arsenide will make some technological process not carry out smoothly.Arsenide will have a strong impact on the quality and the economic benefit of product like this.Therefore the arsenide content in the petroleum hydrocarbon must be controlled within the certain standard.For example, the arsenic content of naphtha product should be less than 20ng/g.For the arsenic people that remove in the petroleum hydrocarbon have carried out long term studies, proposed various arsenic removing methods and prepared various dearsenic agents.
Chinese patent CN1278523A discloses the Catalysts and its preparation method that a kind of normal temperature removes trace arsenide in the hydrocarbon, and this catalyzer is by CuO, ZnO, Al
2O
3Form with precious metal.
Chinese patent CN1030440A relates to the process of removing phosphorus and arsenide from the mixture of hydrocarbon polymer that is generally liquid state or hydrocarbon polymer.In this process, use above-mentioned hydrocarbon polymer and hydrogen to contact with a kind of catalyzer that contains at least 50% metal state nickel.This process can be applicable to the purification of petroleum naphtha and gasoline.
It is γ-Al that Chinese patent CN1294174A discloses a kind of main component
2O
3Dearsenic agent with the silico-aluminate micro porous molecular sieve is applicable to the dearsenification of light-end products such as petroleum naphtha.
Chinese patent CN129820A discloses a kind of method and dearsenification sorbent material that removes arsenic from hydrocarbon ils.This dearsenic agent is made up of free activating oxide carrier and the active ingredient that is selected from copper (zinc) oxide compound, sulfide or sulfuric acid mantoquita.Can under normal temperature condition, remove the arsenide (300ng/g to 10ng/g) in the sulfur-bearing petroleum naphtha.
Because liquid condition petroleum hydrocarbon is formed complicated, so having relatively high expectations to dearsenic agent.All there are problems such as the arsenic capacity is low, water resistance difference in above-mentioned existing dearsenic agent.Inventor herein etc. by CN1580196A to this in addition improvement, the dearsenic agent that a kind of low temperature or normal temperature remove high boiling point arsenide in the liquid condition petroleum hydrocarbon has been proposed.
Successfully synthesizing M41S type mesoporous molecular sieve with Mobil company in 1992 is sign, and in recent years, the mesoporous molecular sieve material has obtained development fast.Above-mentioned mesoporous molecular sieve material has homogeneous and adjustable mesopore aperture, stable skeleton structure, by certain wall thickness and be easy to adulterated unformed skeleton and form and have superiority such as bigger serface and modifiable internal surface, and behaved known by the ultimate principle that template prepares this material.They are often used as catalyzer, sorbent material or support of the catalyst etc., but as far as we know, are suitable for the mesoporous molecular sieve material of liquid condition petroleum hydrocarbon dearsenification system at present, especially at home and abroad do not report by the mesoporous molecular sieve material of direct method preparation.Because the above-mentioned advantage that mesoporous molecular sieve has, if can be used to prepare the liquid condition petroleum hydrocarbon dearsenic agent, bigger specific surface area and bigger central hole structure might be provided, implant after the active ingredient dispersed activity component preferably, can provide bigger passage for the petroleum liquid hydrocarbon fluid, help improving the transmission performance that contains arsenic liquid condition petroleum hydrocarbon medium, thereby improve the normal temperature low temperature dearsenification performance of liquid condition petroleum hydrocarbon.
Although US20040050795A1 has announced that a kind of mesoporous molecular sieve with high-sequential is a carrier, the load lanthanide series metal is used for removing the arsenate of fluid, and this dearsenic agent has highly selective, quick and high loading capacity, but this patent only limits to current and the dearsenification of gaseous state fluidic, and the arsenide in the fluid only is confined to inorganic arsenide, and is well-known, the adsorbing and removing character of organoarsenic and inorganic arsenic is diverse, and is also different fully to the design requirements of dearsenic agent material.Therefore intimate blank about the research of mesoporous molecular sieve base fluid attitude petroleum hydrocarbon dearsenification material at present.
Summary of the invention
The objective of the invention is to obtain under normal temperature condition, to have arsenic capacity height, the liquid condition petroleum hydrocarbon dearsenic agent of advantages such as water resistance is good, dearsenification excellent property and preparation method thereof.
One aspect of the present invention provides a kind of liquid condition petroleum hydrocarbon arsenic removal catalyst, described dearsenic agent comprises: the mesoporous molecular sieve that contains the dearsenification active ingredient of 50-99 weight part and the shaping structures subsidiary material of 1-50 weight part, described molecular sieve is silicon-dioxide mesoporous molecular sieve or sial mesoporous molecular sieve, described molecular sieve has the mean pore size of 2-50nm, specific surface area 100m
2/ g～1000m
2/ g; The precursor of described dearsenification active ingredient is selected from a kind of to multiple in the nitrate of copper, iron, manganese, nickel, five kinds of elements of silver or muriate or vitriol or sulfide or the oxalate compound, and the metal gross weight percentage composition of described precursor in dearsenic agent is 0.01～20%.
In the preference of the present invention, the precursor of described active ingredient is a kind of to multiple in the nitrate of copper and/or silver or muriate or vitriol or sulfide or the oxalate compound, the metal gross weight percentage composition of described precursor in dearsenic agent is preferred 1～15%, and more preferably 3～10%.
In the preference of the present invention, the precursor of described active ingredient is selected from: cupric chloride, cupric nitrate, copper sulfate, cuprous chloride, cupric oxalate, Silver Nitrate or its mixture.
In the preference of the present invention, described mesoporous molecular sieve has the mean pore size of 3-15nm, and specific surface area is 200m
2/ g～800m
2/ g.
Another aspect of the present invention provides a kind of preparation method of liquid condition petroleum hydrocarbon arsenic removal catalyst, comprise the steps: that (i) carries out mesoporous molecular sieve and active ingredient precursor compound, wherein said mesoporous molecular sieve has the mean pore size of 2-50nm, specific surface area 100m
2/ g～1000m
2/ g; (ii) add the shaping structures agent and carry out moulding, drying; (iii), obtain dearsenic agent 200-700 ℃ of following thermal treatment 0.5-12 hour (preferably 0.5-6 hour).
In the preference of the present invention, the mesoporous molecular sieve in the described step (i) adopts the organic or inorganic silicon and aluminum source synthetic under the structure directing agent effect.
In the preference of the present invention, what complex method adopted in the described step (i) is the load method preparation, or it is compound to adopt direct method to carry out in synthetic mesoporous molecular sieve.
In the preference of the present invention, described structure directing agent is ethylene oxide-propylene oxide copolymer and/or alkyl substituted benzene, the ethylene oxide of preferred molecular weight 2000～10000-propylene oxide copolymer polymkeric substance and/or trialkyl substituted, the more preferably ethylene oxide of molecular weight 2000～6000-propylene oxide random copolymers and/or trialkyl substituted, described alkyl is C
1-C
8Alkyl.
A further aspect of the invention provides a kind of purposes of liquid condition petroleum hydrocarbon arsenic removal catalyst, and it is used for the dearsenification of liquid condition petroleum hydrocarbon.
Embodiment
The inventor is through extensive and deep research, by improving preparation technology, prepared on molecular sieve load by the dearsenic agent of dearsenification active ingredient, and be surprised to find that this dearsenic agent can remove arsenide in the liquid condition petroleum hydrocarbon under the water content conditions of higher fast in normal temperature, high-speed, oil product, thereby can be used as the dearsenic agent of the dearsenicating technology of liquid oil products such as petroleum naphtha, pyrolysis gasoline.Finished the present invention on this basis.
The mesoporous molecular sieve material
Molecular screen material can be silicon-dioxide mesoporous molecular sieve or sial mesoporous molecular sieve.The mesoporous molecular sieve material can adopt organic silicon and aluminum source synthetic under the structure directing agent effect, also can adopt the inorganic silicon-aluminum source synthetic under same condition.Silicon and aluminum source can be this area various silicon and aluminum sources commonly used, preferred TEOS, NaAlO
2, in alkali metal silicate salt hydrate and the aluminum isopropylate one or more, the preferred Na of alkali metal silicate salt hydrate
2SiO
39H
2O.Can adopt ethylene oxide-propylene oxide copolymer and/or alkyl substituted benzene in the synthetic method is structure directing agent, ethylene oxide-the propylene oxide copolymer of preferred molecular weight 2000～10000 and/or trialkyl substituted, the more preferably ethylene oxide of molecular weight 2000～6000-propylene oxide random copolymers and/or three (C
1-C
8Alkyl) substituted benzene.
Active ingredient
Active ingredient of the present invention is the metal ion that has the precursor of active ingredient to form after calcination.In the present invention, main active ingredient for example, at copper, iron, manganese, nickel, the nitrate of five kinds of elements of silver or the ion of muriate or vitriol or sulfide or copper, iron, manganese, nickel or the silver element of oxalate compound (or its mixture) after calcination in the formed mixture.
The preferred example that is used for the precursor of active ingredient of the present invention comprises: cupric chloride, cupric nitrate, copper sulfate, cuprous chloride, cupric oxalate, Silver Nitrate or its mixture.
In the present invention, load the mesoporous molecular sieve of dearsenification active ingredient be generally the 50-99 weight part, preferably be the 60-95 weight part.
The active ingredient of molecular screen material can adopt the load method preparation, also can adopt direct method preparation in synthetic mesoporous molecular sieve to contain the mesoporous molecular sieve material of active ingredient.
In a preference, load method divides following several steps to finish: preparation mesoporous molecular sieve material earlier then with this molecular screen material of solution impregnation that contains the active ingredient precursor, evaporates the molecular screen material that must contain active ingredient behind the part moisture.
The shaping structures subsidiary material
The shaping structures subsidiary material are also referred to as the shaping structures agent.Can be used for shaping structures subsidiary material of the present invention and be not particularly limited, can be this area various shaping structures subsidiary material commonly used.
Preferred construction moulding subsidiary material are the oxide solids that contain aluminium or silicon, and these subsidiary material are more preferably from aluminiferous oxide solid.
In dearsenic agent of the present invention, the shaping structures subsidiary material are generally the 1-50 weight part, preferably are the 3-20 weight part.
The present invention also provides the preparation method of dearsenic agent, this method comprises the dearsenification active constituent loading on mesoporous molecular sieve, then load there is the mesoporous molecular sieve of active ingredient to mix and moulding with ordinary method with the shaping structures subsidiary material, at last the green compact of moulding are heat-treated, thereby form dearsenic agent.
In a preference, described preparation method comprises step:
(i) mesoporous molecular sieve and active ingredient precursor are carried out compound, wherein said mesoporous molecular sieve has the mean pore size of about 2-50nm, the about 100m of specific surface area
2/ g～1000m
2/ g;
(ii) add the shaping structures agent and carry out moulding, drying;
(iii), obtain dearsenic agent at about 200-700 ℃ of following thermal treatment 0.5-12 hour.
Compare with existing liquid condition petroleum hydrocarbon dearsenic technique, the present invention has following characteristics:
1. dearsenic agent provided by the invention adapts to the liquid condition petroleum hydrocarbon with extensive character, and the complicated composition in the petroleum hydrocarbon is had good adaptability.
2. dearsenic agent provided by the invention has the dearsenification capacity (optimum condition can reach more than 1.6%) near the hydro-dearsenic catalyst level.
3. dearsenic agent provided by the invention can fundamentally improve the transmission performance that contains arsenic liquid condition petroleum hydrocarbon medium, can improve dearsenification usefulness under normal temperature, lower temperature condition.
4. dearsenic agent provided by the invention can be removed the arsenide in the liquid condition petroleum hydrocarbon fast under normal temperature condition, can adapt to change bigger working condition.
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Ratio and per-cent are based on weight, unless stated otherwise.
Embodiment 1
The molecular sieve preparation
300mL water and 1200 gram 2M combined are placed in 40 ℃ the water-bath heating and stir.In this solution, add 40.0 gram ethylene oxide-propylene oxide copolymers, (available from Aldrich company, molecular-weight average 4000, be designated as S123, down together), continuing to be stirred to solution is clear solution, then 91.0mLTEOS (positive tetraethyl orthosilicate) dropwise is added drop-wise in the above-mentioned solution, after dropwising this solution stirring 20h is obtained white casse liquid, this mixture is joined in the teflon-lined crystallizing kettle 80 ℃ of following crystallization 24 hours. the solid matter of gained is filtered and washs to filtrate and do not have chlorion with the glass sand core funnel, behind 550 ℃ of thermal treatment 4h, obtain white powder.The mean pore size of gained mesoporous molecular sieve material is 6 ± 2nm, and specific surface area is 540m
2/ g, pore volume are 0.8 mL/g.
The dearsenic agent preparation
Take by weighing 1.29 gram Cu (NO
3)
23H
2O is dissolved in 100 gram water, adding above-mentioned carrier 10.00 restrains in the above-mentioned copper nitrate aqueous solution, stirring makes and mixes, and under agitation heating evaporates part moisture, can obtain light blue pulverulent solids thing, add the 2.00g pseudo-boehmite as the shaping structures agent after thorough mixing, extrusion moulding, the gained extrudate is after 120 ℃ of dryings, thermal treatment 6h under 350 ℃ of conditions promptly gets dearsenic agent again.
The dearsenification performance test
In the Erlenmeyer flask of 60mL, be weighed into the 1.0g catalyzer, add the petroleum naphtha (containing arsenic concentration is 500 μ g/mL) that 50mL is furnished with the triethyl arsine, the sealing of jumping a queue.Erlenmeyer flask is placed on 2 hours after-filtration of reaction in the homothermic oscillator, and filtrate is made the arsenic analysis on Content.According to People's Republic of China's petroleum chemical industry standard (SH/T0629-1996)--POTASSIUM BOROHYDRIDE-Silver Nitrate spectrophotometry carries out arsenic content analysis in the oil product medium, and the arsenic appearance of calculating dearsenic agent according to the concentration difference of front and back is the 21.1gAs/Kg dearsenic agent.
Embodiment 2
Take by weighing the 4.11g aluminum isopropylate, measure positive tetraethyl orthosilicate of 90.0mL and 100mLHCl solution (PH=1.5) and mix, get solution A with magnetic agitation.Take by weighing 40.0gS123 and be dissolved in 1500mL HCl solution (PH=1.5), get solution B with the magnetic agitation mixing.Under 40 ℃ water-baths and agitation condition, solution A is added drop-wise in the solution B, dropwising the back continue to stir after 5 hours and it to be transferred in the teflon-lined crystallizing kettle 100 ℃ of following crystallization 48 hours. with the solid matter of gained with the filtration of glass sand core funnel and wash to filtrate and do not have chlorion, behind 550 ℃ of thermal treatment 4h, obtain white powder, the mean pore size of gained mesoporous molecular sieve material is 7 ± 2nm, and specific surface area is 500m
2/ g, pore volume are 1.1mL/g.
Preparation of Catalyst and dearsenification evaluation are with embodiment 1, and it is the 22.47gAs/Kg dearsenic agent that arsenic holds.
In that the dynamic dearsenification performance of evaluation petroleum hydrocarbon under flow condition on the fixed bed of dearsenic agent is housed, at air speed 2h
-1Condition under, arsenic holds and to be the 16.47gAs/Kg dearsenic agent, outlet arsenic concentration＜20ppb.
Embodiment 3
Except that the aluminum isopropylate consumption was 8.22g, all the other mean pore sizes with embodiment 2 gained carriers were 7 ± 2nm, and specific surface area is 490m
2/ g, pore volume are 1.0mL/g.It is the 24.64gAs/Kg dearsenic agent that arsenic holds, dynamically arsenic appearance＞16gAs/Kg dearsenic agent.
Embodiment 4
300 gram water and 1200 gram 2M combined are placed in 40 ℃ the water-bath heating and stir.In this solution, add 40.0 gram S123 (ethylene oxide-propylene oxide copolymers, molecular-weight average 4000), continuing to be stirred to solution is clear solution, 91.0mLTEOS is added drop-wise in the above-mentioned solution then, after dropwising this solution stirring 1h is obtained white casse liquid, the filter cake that obtains after this solution filtration is dissolved in the solution that contains 300 gram water and 1200 gram 2M hydrochloric acid and 20.0 gram S123 again, and continue to stir 24 hours down after in this solution, adding the 20.0g Three methyl Benzene at 40 ℃, obtain white casse liquid, this muddy liquid is transferred in the teflon-lined crystallizing kettle 130 ℃ of following crystallization 24 hours. the solid matter of gained is filtered and washs to filtrate and do not have chlorion with the glass sand core funnel, behind 550 ℃ of thermal treatment 4h, obtain white powder, the mean pore size of gained mesoporous molecular sieve material is 10 ± 2nm, and specific surface area is 460m
2/ g, pore volume are 1.7mL/g.
Preparation of Catalyst and dearsenification evaluation are with embodiment 1, and it is the 21.95gAs/g dearsenic agent that arsenic holds.
On the evaluating apparatus that flows, estimate dynamic dearsenification performance, at air speed 2h
-1Condition under, arsenic appearance＞16gAs/Kg dearsenic agent, the outlet arsenic concentration＜20ppb.
Embodiment 5
200 mL water and 1200 gram 2M combined are placed in 40 ℃ the water-bath heating and stir.In this solution, add 40.0 gram M123 (available from Aldrich company, ethylene oxide-propylene oxide copolymer, molecular-weight average 8000), continuing to be stirred to solution is clear solution, then 91.0mLTEOS dropwise is added drop-wise in the above-mentioned solution, after dropwising this solution stirring 20h is obtained white casse liquid, add 10%CuCl again
2Solution 100mL, fully stir 5h, the gained mixture is joined in the teflon-lined crystallizing kettle 80 ℃ of following crystallization 24 hours. the solid matter of gained is filtered and washs to filtrate and do not have chlorion with the glass sand core funnel, behind 550 ℃ of thermal treatment 4h, obtain pulverulent solids.The mean pore size of gained mesoporous molecular sieve material is 7 ± 2nm, and specific surface area is 520m
2/ g, pore volume are 0.9mL/g.
The mesoporous molecular sieve material of gained being implanted the active ingredient precursor is according to embodiment 1 method moulding, and the dearsenification performance is estimated in activation, and it is the 22.05gAs/Kg dearsenic agent that the arsenic of gained dearsenic agent holds.
Embodiment 6
TEOS changes the Na of same molar weight among the embodiment 1
2SiO
39H
2O 115.8g, all the other are tested by embodiment 1, and it is the 21.45gAs/Kg dearsenic agent that the arsenic of gained dearsenic agent holds.
Embodiment 7
TEOS changes same molar weight Na among the embodiment 5
2SiO
39H
2O 115.8g, all the other are tested by embodiment 5, and it is the 21.75gAs/Kg dearsenic agent that the arsenic of gained dearsenic agent holds.
Embodiment 8
Aluminum isopropylate changes same molar weight NaAlO among the embodiment 2
21.65g all the other are tested by embodiment 2, it is the 23.08gAs/Kg dearsenic agent that the arsenic of gained dearsenic agent holds.
Embodiment 9
Aluminum isopropylate changes same molar weight NaAlO among the embodiment 2
21.65g TEOS changes same molar weight Na into
2SiO
39H
2All the other test O 114.5g by embodiment 2, and it is the 21.72gAs/Kg dearsenic agent that the arsenic of gained dearsenic agent holds.
Embodiment 10
Cupric nitrate changes 1/5 molar weight Silver Nitrate among the embodiment 1, and all the other are tested by embodiment 1, and it is the 24.18gAs/Kg dearsenic agent that the arsenic of gained dearsenic agent holds.
Embodiment 11
S123 (ethylene oxide-propylene oxide copolymer among the embodiment 1, molecular-weight average 4000) changes P123 into and (take from Aldrich company, ethylene oxide-propylene oxide-ethylene oxide segmented copolymer, molecular-weight average 5800), all the other are tested by embodiment 1, and it is the 22.18gAs/Kg dearsenic agent that the arsenic of gained dearsenic agent holds.
Embodiment 12
Cupric nitrate changes into equimolar amount copper sulfate among the embodiment 1, and all the other are tested by embodiment 1, and it is the 22.14gAs/Kg dearsenic agent that the arsenic of gained dearsenic agent holds.
Embodiment 13
Dearsenic agent among the embodiment 1 is at 250 ℃ CS
2Behind the sulfuration 2hr, all the other carry out the dearsenification performance test by embodiment 1 in the steam, and it is the 18.50gAs/Kg dearsenic agent that the arsenic of gained dearsenic agent holds.
Embodiment 14
Cupric nitrate among the embodiment 1 changes into the copper sulfate of equimolar amount and cupric nitrate mixture, and wherein the ratio of the molar weight of copper sulfate and cupric nitrate is 1: 1, and all the other carry out the dearsenification performance test by embodiment 1, and it is the 20.32gAs/Kg dearsenic agent that the arsenic of gained dearsenic agent holds.
Embodiment 15
Cupric nitrate among the embodiment 1 changes the cupric oxalate with equimolar amount into, and all the other carry out the dearsenification performance test by embodiment 1, and it is the 20.4gAs/kg dearsenic agent that the arsenic of gained dearsenic agent holds.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (12)
1. a liquid condition petroleum hydrocarbon arsenic removal catalyst is characterized in that, described dearsenic agent comprises:
The mesoporous molecular sieve that contains the dearsenification active ingredient of 50-99 weight part and the shaping structures subsidiary material of 1-50 weight part,
Described molecular sieve is silicon-dioxide mesoporous molecular sieve or sial mesoporous molecular sieve, and described molecular sieve has the mean pore size of 2-50nm, specific surface area 100m
2/ g～1000m
2/ g;
The precursor of described dearsenification active ingredient is selected from a kind of to multiple in the nitrate of copper, iron, manganese, nickel, five kinds of elements of silver or muriate or vitriol or sulfide or the oxalate compound, and the metal gross weight percentage composition of described precursor in dearsenic agent is 0.01～20%.
2. dearsenic agent as claimed in claim 1, it is characterized in that, the precursor of described active ingredient is a kind of to multiple in the nitrate of copper and/or silver or muriate or vitriol or sulfide or the oxalate compound, and the metal gross weight percentage composition of described precursor in dearsenic agent is 1～15%.
3. dearsenic agent as claimed in claim 2 is characterized in that, the metal gross weight percentage composition of described precursor in dearsenic agent is 3～10%.
4. dearsenic agent as claimed in claim 1 is characterized in that, the precursor of described active ingredient is selected from: cupric chloride, cupric nitrate, copper sulfate, cuprous chloride, cupric oxalate, Silver Nitrate or its mixture.
5. dearsenic agent as claimed in claim 1 is characterized in that described mesoporous molecular sieve has the mean pore size of 3-15nm, and specific surface area is 200m
2/ g～800m
2/ g.
6. the preparation method of the described liquid condition petroleum hydrocarbon arsenic removal catalyst of claim 1 is characterized in that, comprises the steps:
(i) mesoporous molecular sieve and active ingredient precursor are carried out compound, wherein said mesoporous molecular sieve has the mean pore size of 2-50nm, specific surface area 100m
2/ g～1000m
2/ g;
(ii) add the shaping structures agent and carry out moulding, drying;
(iii), obtain dearsenic agent at 200-700 ℃ of following thermal treatment 0.5-12 hour.
7. method as claimed in claim 6 is characterized in that, the mesoporous molecular sieve in the described step (i) adopts the organic or inorganic silicon and aluminum source synthetic under the structure directing agent effect.
8. method as claimed in claim 6 is characterized in that, what complex method adopted in the described step (i) is the load method preparation, or it is compound to adopt direct method to carry out in synthetic mesoporous molecular sieve.
9. method as claimed in claim 7 is characterized in that, described structure directing agent is ethylene oxide-propylene oxide copolymer and/or alkyl substituted benzene, and described alkyl is C
1-C
8Alkyl.
10. method as claimed in claim 9 is characterized in that, described structure directing agent is the ethylene oxide-propylene oxide copolymer polymkeric substance and/or trialkyl substituted of molecular weight 2000～10000.
11. method as claimed in claim 9 is characterized in that, described structure directing agent is the ethylene oxide-propylene oxide random copolymers and/or trialkyl substituted of molecular weight 2000～6000.
12. the purposes of a liquid condition petroleum hydrocarbon arsenic removal catalyst as claimed in claim 1 is characterized in that, is used for the dearsenification of liquid condition petroleum hydrocarbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100293446A CN100384966C (en) | 2005-09-02 | 2005-09-02 | Liquid state petroleum hydrocarbon normal temperature dearsenicating agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100293446A CN100384966C (en) | 2005-09-02 | 2005-09-02 | Liquid state petroleum hydrocarbon normal temperature dearsenicating agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1923966A CN1923966A (en) | 2007-03-07 |
| CN100384966C true CN100384966C (en) | 2008-04-30 |
Family
ID=37816794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100293446A Expired - Fee Related CN100384966C (en) | 2005-09-02 | 2005-09-02 | Liquid state petroleum hydrocarbon normal temperature dearsenicating agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100384966C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591554B (en) * | 2008-05-30 | 2013-05-08 | 北京三聚环保新材料股份有限公司 | Normal temperature compound desulfuration and dearsenization agent and preparation method thereof |
| CN109589762B (en) * | 2018-12-29 | 2021-09-10 | 沈阳三聚凯特催化剂有限公司 | Gas-phase dearsenic agent and preparation method thereof |
| CN110404557A (en) * | 2019-08-16 | 2019-11-05 | 昆明理工大学 | A kind of active carbon fibre Wiki catalyst and its preparation method and application |
| CN111672533B (en) * | 2020-06-28 | 2021-07-13 | 北京化工大学 | Dearsenifying catalyst and its prepn |
| CN115624977B (en) * | 2022-11-11 | 2024-02-13 | 昆山市精细化工研究所有限公司 | Dearsenization agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294174A (en) * | 1999-10-21 | 2001-05-09 | 中国石化集团齐鲁石油化工公司 | Dearse-nicating agent for light oil and its preparing agent |
| US20040050795A1 (en) * | 2002-09-18 | 2004-03-18 | Park Jae Kwang | Removal of arsenic and other anions using novel adsorbents |
-
2005
- 2005-09-02 CN CNB2005100293446A patent/CN100384966C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294174A (en) * | 1999-10-21 | 2001-05-09 | 中国石化集团齐鲁石油化工公司 | Dearse-nicating agent for light oil and its preparing agent |
| US20040050795A1 (en) * | 2002-09-18 | 2004-03-18 | Park Jae Kwang | Removal of arsenic and other anions using novel adsorbents |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1923966A (en) | 2007-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1078104C (en) | Supported catalysts | |
| CN100384966C (en) | Liquid state petroleum hydrocarbon normal temperature dearsenicating agent and preparation method thereof | |
| EP0108610A2 (en) | Method for preparing a zeolite-containing catalyst | |
| RU2506997C1 (en) | Catalyst of recycling heavy oil fractions | |
| CN107303507B (en) | Preparation method of aluminum oxide containing phosphorus and silicon | |
| JP4473450B2 (en) | Nickel catalyst | |
| CN109894122B (en) | FCC gasoline hydrodesulfurization catalyst and preparation method thereof | |
| CN1915486B (en) | Hydrated alumina with structure of similar to thin diaspore of containing additive | |
| CN101157029A (en) | A dicyclopentadiene hydrogenation special-purpose catalyzer and its preparing method | |
| CN1978594B (en) | Liquid-state petroleum hydrocarbon dearsenicing agent with dual medium-hole structure distribution and preparing method thereof | |
| CN1915485B (en) | Alumina containing additive | |
| CN106391097B (en) | Porous ZSM-5 zeolite and γ-Al2O3The synthesis of composite material and prepare Hydrobon catalyst | |
| CN104043477A (en) | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof | |
| US6251823B1 (en) | Production of spherical catalyst carrier | |
| CN102553638B (en) | Double-microporous-mesoporous composite molecular sieve hydrocracking catalyst | |
| CN108855127B (en) | Hydrogenation catalyst and preparation method thereof | |
| RU2527573C1 (en) | Catalyst for processing heavy crude oil material and method of its preparation | |
| CN108201884A (en) | γ-Al2O3The preparation method of carrier and the preparation method of alkane isomerization catalyst | |
| US4764499A (en) | Method for producing dual colloid catalyst composition | |
| CN110614099B (en) | Iron-based Fischer-Tropsch synthesis catalyst, preparation method thereof and Fischer-Tropsch synthesis method | |
| CN1769169A (en) | Beta zeolite granule possessing multiple grade pore passage and its preparation method | |
| CN103785462B (en) | A kind of cycloalkane hydrogenation catalyst and its preparation method and application | |
| CN101173181A (en) | Liquid condition petroleum hydrocarbon arsenic removal catalyst, producing method and use of the same | |
| CN104870085A (en) | Preparation of silica-alumina composition | |
| RU2739560C1 (en) | Method of producing spherical alumina support |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080430 Termination date: 20110902 |