CN101591554B - Normal temperature compound desulfuration and dearsenization agent and preparation method thereof - Google Patents
Normal temperature compound desulfuration and dearsenization agent and preparation method thereof Download PDFInfo
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- CN101591554B CN101591554B CN200810114095.4A CN200810114095A CN101591554B CN 101591554 B CN101591554 B CN 101591554B CN 200810114095 A CN200810114095 A CN 200810114095A CN 101591554 B CN101591554 B CN 101591554B
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Abstract
The invention relates to a desulfuration and dearsenization agent, which comprises a carrier and active components; wherein, the carrier can be formed by a single carrier, or by two or more carriers, and the carrier accounts for 10-80wt% of the total weight of the desulfuration and dearsenization agent; the active components comprises 0.1-40wt% of lead oxide, 0.1-60wt% of magnetic Fe21.333O32 and0.1-40wt% of copper oxide. The invention further discloses a preparation method of the desulfuration and dearsenization agent. The desulfuration and dearsenization agent prepared by the invention has high sulfur capacity and arsenic capacity with desulfuration and dearsenization rate being higher than 99%.
Description
Technical field
The present invention relates to scavenging agent of a kind of dearsenification of desulfurization at normal temperatures and preparation method thereof, particularly a kind of in lighter hydrocarbons normal temperature desulfurating and dearsenic agent and preparation method thereof, belong to chemisorption purification techniques field.
Background technology
As everyone knows, contain various metals impurity and nonmetallic impurity in oil, as iron, nickel, vanadium, copper, lead, sulphur, nitrogen, arsenic etc.In oil is processed refining process, basically most of impurity can be removed, make foreign matter content be reduced to certain level, the trace impurity that still remains in oil inside after processing still inevitably affects grade of oil.For example, after heavier petroleum fraction is carried out cracking (catalytic cracking, catalytic pyrolysis, visbreaking and coking) processing, still contain a lot of sulfocompounds and arsenic compound in the lighter hydrocarbons of producing (light ends); Wherein, sulfocompound hydrogen sulfide (H the most commonly
2S) and mercaptan, may be also carbonylsulfide (COS); The arsenic compound majority is with AsR
3There is (wherein R is a hydrogen atom or alkyl) in form.Above-mentioned lighter hydrocarbons comprise C
1～C
15Various alkane, alkene, alkynes and aromatic hydrocarbon, these lighter hydrocarbons are important fuel and industrial chemicals, but sulfur-bearing or the above-mentioned lighter hydrocarbons that contain arsenic are underproof raw materials; If will contain sulphur or arsenic such as light-end products such as petroleum naphthas as ethylene cracking material, the arsenic impurities of this light-end products inside not only can affect the coke cleaning period of pyrolyzer and the yield of ethene, and may cause and poisoning and poly-unit olefin polymerization catalysis poisoning of hydrogenation catalyst in the follow-up hydrogenation device directly affect quality product; Similarly, sulfur impurity also can exert an influence to the activity of hydrogenation catalyst.So, for fear of the problems referred to above, must carry out desulfurization and dearsenification pre-treatment to above-mentioned lighter hydrocarbons, otherwise it can't directly apply in follow-up Chemical Manufacture.Commonly used can be used for desulfurization and the pretreated reagent of dearsenification is divided into two kinds, a kind ofly be desulfurization and dearsenic catalyst, another is desulfurating and dearsenic agent (being also desulfurization dearsenification scavenging agent).Wherein, desulfurating and dearsenic agent can play by reaction sulfur impurity contained in lighter hydrocarbons and arsenic are removed, and by the subsequent regeneration program, make desulfurating and dearsenic agent regenerate, therefore often select the dearsenification desulfurizing decontaminating agent to carry out desulfurization dearsenification pre-treatment in Chemical Manufacture.
Chinese patent CN1923966A discloses the preparation method of a kind of liquid condition petroleum hydrocarbon arsenic removal catalyst and this dearsenic agent, and this arsenic removal catalyst is by having 2～50nm mean pore size, and specific surface area is 100～1000m
2The silicon-dioxide of/g or sial mesoporous molecular sieve, and be selected from that the nitrate of copper, iron, manganese, nickel, five kinds of elements of silver or one or more the active ingredient in muriate or vitriol or sulfide or oxalate compound consist of.Its preparation method is compound at first hollow molecules sieve and active ingredient precursor being carried out, and the described compound carrier that is about to prepare is put into active component solution, stirs and heats, and after transpiring moisture, obtains the mixture of main minute of activity and carrier; Add afterwards the shaping structures agent fully to mix, also dry after extrusion moulding, and then heat-treated under 200～700 ℃ 0.5～12 hour, can obtain dearsenic agent.This dearsenic agent can be widely used in the dearsenification pre-treatment of normal temperature liquid condition petroleum hydrocarbon.Utilizing the arsenic capacity of the catalyzer that aforesaid method prepares is 16.47～24.64gAs/Kg, is also that its arsenic capacity is only 1.647～2.464wt%.From its reaction principle, it is in the process of preparation dearsenic agent, and so main use or dipping method is its inevitable problem that causes the transition metal solution environmental pollution because steeping fluid is excessive of inevitably having brought.
Chinese patent CN1667091A discloses a kind of liquid condition petroleum hydrocarbon arsenic removal catalyst equally, this dearsenic agent is selected from the 5th or the 6th main group compound of copper, iron, manganese, silver, five kinds of elements of palladium by active ingredient, or in its zero-valent state metal two kinds are composited, and the oxide carrier of the above-mentioned active ingredient of support consists of.This dearsenic agent equally can scalable character liquid condition petroleum hydrocarbon, and also all fine to the adaptability of moisture in petroleum hydrocarbon and sulfide, but the arsenic capacity of this dearsenic agent only can reach 1.5wt%.In addition, what the preparation of this dearsenic agent was adopted is conventional pickling process, uses the method easily to cause transition metal solution to the pollution of environment because steeping fluid is excessive equally.
Although disclosed in above-mentioned two patent documentations is a kind of dearsenic agent, it can play the effect of desulfurization to this dearsenic agent equally as can be known according to its composition.
US Patent No. 5990372 discloses a kind of hydrocarbon stream sorbent material and preparation method thereof, and this sorbent material is made of ferric oxide, manganese oxide and carrier, can remove the trace impurities such as sulphur, arsenic and mercury in hydrocarbon gas.For the preparation of this sorbent material, it can use coprecipitation method, decomposition method, pickling process and mechanical mixing, preferably uses coprecipitation method or decomposition method.
Can find out from above-mentioned prior art document, in normally used dearsenification sweetening agent, mostly adopt be with active constituent loading on carrier in order to realize that it is to the desulfurization dearsenification pre-treatment of lighter hydrocarbons; Wherein, carrier comprises molecular sieve, titanium dioxide, silicon-dioxide, aluminum oxide etc. mostly, the compound of the transition metals such as active ingredient multiselect copper, iron, manganese, silver, palladium, nickel.Wherein, if select iron as active ingredient, the oxide compound Fe of large more options iron in its active compound
2O
3For disclosed desulfurating and dearsenic agent in present prior art, also there is a kind of undesirable state on performance in it, namely the sulfur capacity of this scavenging agent and arsenic capacity are all less, and this just can't realize purpose that lighter hydrocarbons are carried out the desulfurization dearsenification in desulfurization dearsenification preprocessor.In addition, for the preparation method of desulfurating and dearsenic agent, it mainly comprises pickling process, coprecipitation method, decomposition method, mechanical mixing etc.; But in the prior art, that mostly adopt for the preparation of above-mentioned desulfurating and dearsenic agent is all single preparation method, the deficiency that its method existence itself is arranged due to various preparation methods, more or less on product characteristics generation impact to a certain degree, so will stabilize and increase to a great extent product performance if can effectively the preparation method be coupled to prepare desulfurating and dearsenic agent.
Summary of the invention
Technical problem to be solved by this invention is that Sulfur capacity and the arsenic appearance of desulfurating and dearsenic agent in prior art is lower, and owing to using the unitary system Preparation Method to cause the unstable properties of desulfurating and dearsenic agent, i.e. desulfurization dearsenification efficient is not high; On this basis, provide a kind of and have that higher sulfur capacity and arsenic hold, the desulfurization arsenic-removing rate is up to the desulfurating and dearsenic agent more than 99%, and the coupling preparation for preparing this desulfurating and dearsenic agent further is provided.
For solving the problems of the technologies described above, the invention provides a kind of desulfurating and dearsenic agent, this desulfurating and dearsenic agent is made of carrier and active ingredient; Described active ingredient is plumbous oxide 0.1～40wt%, martial ethiops Fe
21.333O
320.1～60wt%, cupric oxide are 0.1～40wt%; Described carrier accounts for 10～80wt% of desulfurating and dearsenic agent gross weight.
Wherein, in preferred described active ingredient, plumbous oxide content is 0.1～20wt%, and most preferably plumbous oxide content is 5～20wt%; Martial ethiops Fe in preferred described active ingredient
21.333O
32Content is 0.1～40wt%, most preferably martial ethiops Fe
21.333O
32Content is 20～40wt%; In preferred described active ingredient, cupric oxide content is 0.1～20wt%, and most preferably cupric oxide content is 0.1～10wt%.In preferred described desulfurating and dearsenic agent, the content of carrier is 10～60wt%, and most preferably its content is 20～40wt%.
Wherein, described carrier is γ-Al
2O
3The specific surface area of described carrier is 20～350m
2/ g, pore volume are 0.1～20cm
3/ g.For specific surface area and the pore volume of described carrier, the specific surface area of preferred described carrier is 60～300m
2/ g, pore volume are 0.3～1.2cm
3/ g.
Carrier of the present invention can be that a kind of carrier can be also the combination of variety carrier; Described single carrier can be selected from aluminum oxide, ZSM-5 molecular sieve, neutral molecule sieve, gac, silicon-dioxide, titanium dioxide, sieve and silica-sesquioxide.
The present invention also disclosing on the basis of above-mentioned desulfurating and dearsenic agent, further discloses the preparation method of above-mentioned desulfurating and dearsenic agent, and it comprises the steps:
(1) adopt " doing " to soak method, carrier impregnation in active ingredient lead salt solution, was flooded 0.5～3 hour;
(2) will flood carrier after lead salt, 100～120 ℃ of dryings 1～5 hour; With the carrier after load lead salt after drying equally under aerobic conditions, in 400～900 ℃ of lower calcination activations 3～10 hours;
(3) go solution to mix the iron salt solutions of solubility and mantoquita, and fully stir it is mixed, then to above-mentioned mixed solution and dripping sodium carbonate or sodium hydroxide solution, the pH value to 7.2 of regulator solution～7.6 generate the throw out of iron, copper simultaneously;
(4) throw out that obtains in step (3) is carried out nature and place ageing, be 0.5～8 hour storage period; Afterwards throw out is washed and filters;
(5) product that step (4) is obtained and carrier mix, and fully kneading is 0.5～1 hour;
(6) product that obtains in the product that obtains in described step (2) and step (5) was carried out kneading 1～3 hour, extrusion or roller forming also carry out drying, afterwards under aerobic conditions, in 300～900 ℃ of lower calcination activations 3～10 hours, namely obtain desulfurating and dearsenic agent.
Wherein, described lead salt is plumbic acetate.Carry out drying in described step (2) under aerobic conditions; In roasting process, maturing temperature is 500～650 ℃, and soak time is 5～8 hours.PH value in described step (3) is 7.4; Being warming up to 60～85 ℃ when regulating pH value reacts.In described step (6), drying temperature is 105～110 ℃, and be 1～3 hour time of drying; Preferred maturing temperature is 350～650 ℃, and soak time is 4～8 hours.
In preparation during above-mentioned desulfurating and dearsenic agent, use be that " doing " soaks the preparation method that method, coprecipitation method and kneading method are coupled.The present invention at first use " doing " soak method in addition follow-up calcination procedure realized the dispersion of active ingredient plumbous oxide (PbO) on carrier; Wherein, described " doing " method of soaking is on the basis of the water regain that calculates selected carrier, determining can be by flooding the disposable amount that is carried on the active ingredient on described carrier, thereby make carrier once steeping fluid to be absorbed, avoided the generation of active ingredient waste liquid, environmentally friendly.Afterwards, the present invention continues to adopt coprecipitation method, by selecting rational co-precipitation reagent, realizes the coprecipitation of copper, iron in desulfurating and dearsenic agent active ingredient of the present invention, thus the even mixing of copper throw out and iron precipitate; On this basis, add appropriate carrier in mixed uniformly copper throw out and iron precipitate, by kneading method, make above-mentioned copper throw out and the iron precipitate can uniform loading and be scattered on carrier.At last, again adopt kneading method, load there is the carrier of active ingredient PbO and has the carrier of copper throw out and iron precipitate to mix by the load that coprecipitation method and kneading method prepare, the kneading certain hour, and dry, calcination activation, copper throw out and iron precipitate are decomposed, thereby realized the effective dispersion on carrier of active ingredient cupric oxide and ferric oxide; In this step, maturing temperature is a very crucial technical essential, and the selection of suitable maturing temperature is conducive to obtain the martial ethiops Fe described in the present invention
21.333O
32, and the growth of the complete crystalline form of each active ingredient, thus guarantee provided for the activity that improves desulfurating and dearsenic agent; In addition, use this kneading method to avoid on the one hand the generation of waste liquid, also reduced on the other hand the burden of washing in the preparation procedure, improved the preparation efficiency of desulfurating and dearsenic agent.
The present invention has advantages of as described below:
(1) desulfurating and dearsenic agent of the present invention uses martial ethiops, plumbous oxide and cupric oxide as the active ingredient that is carried on carrier, can obtain having greater than the Sulfur capacity of 15wt% and the desulfurating and dearsenic agent of arsenic appearance by the ratio of component of controlling above-mentioned active ingredient, and the desulfurization dearsenification efficient of this desulfurating and dearsenic agent is up to more than 99%.
(2) the present invention adopts the preparation method of dry immersion, coprecipitation method and kneading method coupling to prepare desulfurating and dearsenic agent of the present invention; Wherein, use dry immersion, the water regain of the carrier by calculating choice for use can be controlled the amount of steeping fluid effectively, guarantees that steeping fluid fully enters carrier inside and do not have remaining steeping fluid residual, has reduced the pollution of the residual waste liquid of steeping fluid to environment; The use coprecipitation method can obtain the coprecipitation thing of active element in active ingredient, and the throw out ratio of mixture is more even, with the abundant kneading of it and carrier, can realize the abundant dispersion of described active element throw out on carrier; Use kneading method to have the carrier of active ingredient and load to have the sedimentary carrier of active element fully to mix with above-mentioned through load, thereby guarantee better the uniform loading of uniform active ingredient on carrier, in addition, use this preparation method not have the generation of waste liquid or filtered liquid, environmentally friendly.
Description of drawings
Fig. 1 is martial ethiops Fe of the present invention
21.333O
32XRD spectra.
Embodiment
Embodiment 1
Choose 80 orders, specific surface area is 300m
2/ g, pore volume are 10cm
3Microballoon γ-Al of/g
2O
3Carrier 9.9g puts into the plumbic acetate solution (Pb (Ac) of 100ml 0.89mol/L
23H
2O) in, flood and made the active acetate lead solution fully enter microsphere supported inside in 3 hours; Due to the amount of steeping fluid be according to carrier, the specific absorption of active ingredient is calculated selected, so described activity component impregnation liquid can disposable immersion described microsphere supported inside, can residual any plumbic acetate waste liquid.After above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 5 hours under 100 ℃, removes the moisture in carrier; Again load after drying there is afterwards the γ-Al of plumbic acetate
2O
3Carrier in 400 ℃ of lower calcination activations 10 hours, makes plumbic acetate solution decompose under aerobic conditions, and and then obtains γ-Al that load has the PbO active ingredient
2O
3Carrier.In said process, when the carrier after the steeping fluid dipping is carried out drying, preferred ambient is aerobic environment; Why will carry out drying and calcination activation to the carrier after the active component solution dipping under aerobic conditions, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, and this product covers collection at carrier surface, forms carbon distribution; Assurance just because of aerobic conditions, a small amount of C that pyrolytic decomposition can be obtained generates air release under aerobic environment, thereby the active spaced point that guarantees the active ingredient of carrier surface can fully contact with arsenic compound with sulphur compound and carry out absorption reaction, has guaranteed that further the desulfurization dearsenification of desulfurating and dearsenic agent is active.In addition, selecting maturing temperature is in order to realize better the Uniform Dispersion of active ingredient on carrier.
The ferric chloride Solution of 100ml0.12mol/L and the copper nitrate solution of 1000ml0.5mol/L are mixed, and fully stirring mixes it, then to the sodium carbonate solution of above-mentioned mixed solution and dripping 2000ml0.5mol/L, the pH value that guarantees solution is 7.2, thereby has obtained copper carbonate and iron carbonate throw out.Mentioned solution is carried out nature place ageing 0.5 hour, thereby guarantee that the throw out that reaction generates fully precipitates; Afterwards, use deionized water that above-mentioned throw out is washed and filters, the throw out after washing is separated; Above-mentioned washing times is with final Na
+Content in wash solution gets final product lower than 5ppm.Be 300m with above-mentioned copper carbonate and iron carbonate presoma and 10g after washing less than 80 orders, specific surface area
2/ g, pore volume are 10cm
3Microballoon γ-Al of/g
2O
3Carrier mixes, and kneading 0.5 hour.
γ-the Al that above-mentioned load is had the PbO active ingredient
2O
3Carrier and load have the γ-Al of copper carbonate and iron carbonate
2O
3Carrier carried out kneading 1 hour, after extruded moulding, with this forming composition under 105 ℃ dry 3 hours, under aerobic conditions, under 300 ℃, forming composition was after drying carried out calcination activation 10 hours afterwards, made the iron carbonate throw out be converted into martial ethiops Fe
21.333O
32, the copper carbonate throw out is converted into cupric oxide, thereby obtains containing active ingredient plumbous oxide 40wt%, martial ethiops Fe
21.333O
320.1wt%, cupric oxide are 40wt%, γ-Al
2O
3The desulfurating and dearsenic agent of 19.9wt%.
Embodiment 2
Choose 60 orders, specific surface area is 20m
2/ g, pore volume are 0.1cm
3Microballoon γ-Al of/g
2O
3Carrier 0.066g puts into the plumbic acetate solution (Pb (Ac) of 1000ml0.18mol/L
23H
2O) in, flood and made the active acetate lead solution fully enter microsphere supported inside in 1 hour; Due to the amount of steeping fluid be according to carrier, the specific absorption of active ingredient is calculated selected, so described activity component impregnation liquid can disposable immersion described microsphere supported inside, can residual any plumbic acetate waste liquid.After above-mentioned steeping fluid immerses carrier fully, carrier is taken out, under aerobic conditions under 120 ℃ dry 1 hour, remove the moisture in carrier; Again load after drying there is afterwards the γ-Al of plumbic acetate
2O
3Carrier in 650 ℃ of lower calcination activations 5 hours, makes plumbic acetate decompose under aerobic conditions, and and then obtains γ-Al that load has the PbO active ingredient
2O
3Carrier.In said process, when the carrier after the steeping fluid dipping is carried out drying, preferred ambient is aerobic environment; Why will carry out drying and calcination activation to the carrier after the active component solution dipping under aerobic conditions, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, and this product covers collection at carrier surface, forms carbon distribution; Assurance just because of aerobic conditions, a small amount of C that pyrolytic decomposition can be obtained generates air release under aerobic environment, thereby the active spaced point that guarantees the active ingredient of carrier surface can fully contact with arsenic compound with sulphur compound and carry out absorption reaction, has guaranteed that further the desulfurization dearsenification of desulfurating and dearsenic agent is active.
The solution of ferrous chloride of 1000ml0.285mol/L and the copper-bath of 1ml 0.47mol/L are mixed, and fully stirring mixes it, then to the sodium carbonate solution of above-mentioned mixed solution and dripping 100ml0.4mol/L, the pH value that guarantees solution is 7.4, thereby generates copper carbonate and iron protocarbonate throw out.Above-mentioned throw out solution is carried out nature place ageing 5 hours, thereby guarantee that the throw out that reaction generates fully precipitates; Afterwards, use deionized water that above-mentioned throw out is washed and filters, the throw out after washing is separated; Above-mentioned washing times is with final Na
+Content in wash solution gets final product lower than 5ppm.Be 20m with above-mentioned copper carbonate and iron protocarbonate presoma and 14.94g 60 orders, specific surface area after washing
2/ g, pore volume are 0.1cm
3Microballoon γ-Al of/g
2O
3Carrier mixes, and kneading 1.0 hours.
γ-the Al that above-mentioned load is had the PbO active ingredient
2O
3Carrier and load have the γ-Al of copper carbonate and iron protocarbonate
2O
3Carrier carried out kneading 3 hours, after extruded moulding, with this forming composition under 110 ℃ dry 1 hour, under aerobic conditions, under 650 ℃, forming composition was after drying carried out calcination activation 4 hours afterwards, made the iron carbonate throw out be converted into martial ethiops Fe
21.333O
32, the copper carbonate throw out is converted into cupric oxide, thereby obtains containing active ingredient plumbous oxide 0.1wt%, martial ethiops Fe
21.333O
3260wt%, cupric oxide are 0.1wt%, γ-Al
2O
3The desulfurating and dearsenic agent of 39.8wt%.Need to prove, under aerobic conditions, forming composition is after drying carried out roasting, the ferrous compound oxidation can be made it remain on the valence state of iron in required desulfurating and dearsenic agent product.
Embodiment 3
Choose 120 orders, specific surface area is 350m
2/ g, pore volume are 20cm
3The gac 3g of/g puts into the plumbic acetate solution (Pb (Ac) of 100ml 0.893mol/L
23H
2O) in, flood and made the active acetate lead solution fully enter microsphere supported inside in 2.5 hours; Due to the amount of steeping fluid be according to carrier, the specific absorption of active ingredient is calculated selected, so described activity component impregnation liquid can disposable immersion described microsphere supported inside, can residual any plumbic acetate waste liquid.After above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 2.5 hours under 110 ℃, removes the moisture in carrier; The gac that load that afterwards again will be after drying has plumbic acetate in 500 ℃ of lower calcination activations 8 hours, makes plumbic acetate decompose under aerobic conditions, and and then obtains the absorbent charcoal carrier that load has the PbO active ingredient.In said process, when the carrier after the steeping fluid dipping is carried out drying, preferred ambient is aerobic environment; Why will carry out drying and calcination activation to the carrier after the active component solution dipping under aerobic conditions, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, and this product covers collection at carrier surface, forms carbon distribution; Assurance just because of aerobic conditions, a small amount of C that pyrolytic decomposition can be obtained generates air release under aerobic environment, thereby the active spaced point that guarantees the active ingredient of carrier surface can fully contact with arsenic compound with sulphur compound and carry out absorption reaction, has guaranteed that further the desulfurization dearsenification of desulfurating and dearsenic agent is active.
The ferric chloride Solution of 1000ml 0.25mol/L and the copper nitrate solution of 100ml1.25mol/L are mixed, and fully stirring mixes it, then to the sodium carbonate solution of above-mentioned mixed solution and dripping 1000ml0.375mol/L, the pH value that guarantees solution is 7.6, and heat to 60 ℃, thereby generate copper carbonate and iron carbonate throw out.Above-mentioned throw out solution is carried out nature place ageing 5.0 hours, thereby guarantee that the throw out that reaction generates fully precipitates; Afterwards, use deionized water that above-mentioned throw out is washed and filters, the throw out after washing is separated, can get copper carbonate and iron carbonate; Above-mentioned washing times is with final Na
+Content in wash solution gets final product lower than 5ppm.Be 350m with above-mentioned copper carbonate and iron carbonate presoma and 47g 120 orders, specific surface area after washing
2/ g, pore volume are 20cm
3The gac of/g mixes, and kneading 0.6 hour.Heating in the above-mentioned copper carbonate of preparation and the sedimentary process of iron carbonate is in order to improve the speed of reaction, to promote above-mentioned sedimentary generation; But the selection of this temperature again can not be too high, the too high decomposition that easily causes reactant or product.
There are the gac of PbO active ingredient and gac that load has copper carbonate and iron carbonate to carry out kneading 1.5 hours above-mentioned load, after roller forming, with this forming composition under 108 ℃ dry 2 hours, afterwards under aerobic conditions, under 900 ℃, forming composition is after drying carried out calcination activation 3 hours, make the iron carbonate throw out be converted into martial ethiops Fe
21.333O
32, the copper carbonate throw out is converted into cupric oxide, thereby obtains containing active ingredient plumbous oxide 20wt%, martial ethiops Fe
21.333O
3220wt%, cupric oxide are the desulfurating and dearsenic agent of 10wt%, absorbent charcoal carrier 50wt%.
Embodiment 4
Choose 120 orders, specific surface area is 350m
2/ g, pore volume are 20cm
3Microballoon γ-Al of/g
2O
3Carrier 15g puts into the plumbic acetate solution (Pb (Ac) of 100ml 0.223mol/L
23H
2O) in, flood and made the active acetate lead solution fully enter microsphere supported inside in 2.5 hours; Due to the amount of steeping fluid be according to carrier, the specific absorption of active ingredient is calculated selected, so described activity component impregnation liquid can disposable immersion described microsphere supported inside, can residual any plumbic acetate waste liquid.After above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 2.5 hours under 110 ℃, removes the moisture in carrier; Again load after drying there is afterwards the γ-Al of plumbic acetate
2O
3Under aerobic conditions, in 500 ℃ of lower calcination activations 8 hours, make plumbic acetate decompose, and and then obtain the absorbent charcoal carrier that load has the PbO active ingredient.In said process, when the carrier after the steeping fluid dipping is carried out drying, preferred ambient is aerobic environment; Why will carry out drying and calcination activation to the carrier after the active component solution dipping under aerobic conditions, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, and this product covers collection at carrier surface, forms carbon distribution; Assurance just because of aerobic conditions, a small amount of C that pyrolytic decomposition can be obtained generates air release under aerobic environment, thereby the active spaced point that guarantees the active ingredient of carrier surface can fully contact with arsenic compound with sulphur compound and carry out absorption reaction, has guaranteed that further the desulfurization dearsenification of desulfurating and dearsenic agent is active.
The ferric chloride Solution of 100ml 0.6mol/L and the copper nitrate solution of 59ml2.14mol/L are mixed, and fully stirring mixes it, then to the sodium hydroxide solution of above-mentioned mixed solution and dripping 1000ml0.43mol/L, the pH value that guarantees solution is 7.6, and be warming up to 85 ℃, thereby copper hydroxide and bulky ferric hydroxide precipitate have been obtained.Above-mentioned throw out solution is carried out nature place ageing 5.0 hours, thereby guarantee that the throw out that reaction generates fully precipitates; Afterwards, use deionized water that above-mentioned throw out is washed, at last washings is filtered, the throw out after washing is separated, obtain copper hydroxide and bulky ferric hydroxide precipitate; Above-mentioned washing times is with final Na
+Content in wash solution gets final product lower than 5ppm.Be 350m with above-mentioned copper hydroxide and bulky ferric hydroxide precipitate and 65g 120 orders, specific surface area after washing
2/ g, pore volume are 20cm
3The gac of/g mixes, and kneading 0.6 hour.
Microballoon γ-the Al that above-mentioned load is had the PbO active ingredient
2O
3Carrier and load have the gac of copper hydroxide and ironic hydroxide to carry out kneading 1.5 hours, after roller forming, with this forming composition under 108 ℃ dry 2 hours, afterwards under aerobic conditions, under 350 ℃, forming composition is after drying carried out calcination activation 8 hours, make bulky ferric hydroxide precipitate be converted into martial ethiops Fe
21.333O
32, hydroxide deposits is converted into cupric oxide, thereby can obtain containing active ingredient plumbous oxide 5wt%, martial ethiops Fe
21.333O
325wt%, cupric oxide are the desulfurating and dearsenic agent of 10wt%, carrier 80wt%.
Embodiment 5
Choose 120 orders, specific surface area is 200m
2/ g, pore volume are 20cm
3The gac 3.6g of/g puts into the plumbic acetate solution (Pb (Ac) of 40ml 0.893mol/L
23H
2O) in, flood and made the active acetate lead solution fully enter microsphere supported inside in 0.5 hour; Due to the amount of steeping fluid be according to carrier, the specific absorption of active ingredient is calculated selected, so described activity component impregnation liquid can disposable immersion described microsphere supported inside, can residual any plumbic acetate waste liquid.After above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 2.5 hours under 110 ℃, removes the moisture in carrier; The gac that load that afterwards again will be after drying has plumbic acetate in 500 ℃ of lower calcination activations 8 hours, makes plumbic acetate decompose under aerobic conditions, and and then obtains the absorbent charcoal carrier that load has the PbO active ingredient.In said process, when the carrier after the steeping fluid dipping is carried out drying, preferred ambient is aerobic environment; Why will carry out drying and calcination activation to the carrier after the active component solution dipping under aerobic conditions, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, and this product covers collection at carrier surface, forms carbon distribution; Assurance just because of aerobic conditions, a small amount of C that pyrolytic decomposition can be obtained generates air release under aerobic environment, thereby the active spaced point that guarantees the active ingredient of carrier surface can fully contact with arsenic compound with sulphur compound and carry out absorption reaction, has guaranteed that further the desulfurization dearsenification of desulfurating and dearsenic agent is active.
The ferric chloride Solution of 1000ml 0.15mol/L and the copper nitrate solution of 173ml1.07mol/L are mixed, and fully stirring mixes it, then to the sodium carbonate solution of above-mentioned mixed solution and dripping 1000ml0.25mol/L, the pH value that guarantees solution is 7.6, and heat to 60 ℃, thereby generate copper carbonate and iron carbonate throw out.Above-mentioned throw out solution is carried out nature place ageing 5.0 hours, thereby guarantee that the throw out that reaction generates fully precipitates; Afterwards, use deionized water that above-mentioned throw out is washed and filters, the throw out after washing is separated, can get copper carbonate and iron carbonate; Above-mentioned washing times is with final Na
+Content in wash solution gets final product lower than 5ppm.Be 200m with above-mentioned copper carbonate and iron carbonate throw out and 56.4g 120 orders, specific surface area after washing
2/ g, pore volume are 20cm
3The gac of/g mixes, and kneading 0.6 hour.Heating in the above-mentioned copper carbonate of preparation and the sedimentary process of iron carbonate is in order to improve the speed of reaction, to promote above-mentioned sedimentary generation; But the selection of this temperature again can not be too high, the too high decomposition that easily causes reactant or product.
There are the gac of PbO active ingredient and gac that load has copper carbonate and iron carbonate to carry out kneading 1.5 hours above-mentioned load, after roller forming, with this forming composition under 108 ℃ dry 2 hours, afterwards under aerobic conditions, under 900 ℃, forming composition is after drying carried out calcination activation 3 hours, make the iron carbonate throw out be converted into martial ethiops Fe
21.333O
32, the copper carbonate throw out is converted into cupric oxide, thereby obtains containing active ingredient plumbous oxide 8wt%, martial ethiops Fe
21.333O
3212wt%, cupric oxide are the desulfurating and dearsenic agent of 20wt%, carrier 60wt%.
Embodiment 6
Choose 80 orders, specific surface area is 150m
2/ g, pore volume are 10cm
3Microballoon γ-Al of/g
2O
3Carrier 19g puts into the plumbic acetate solution (Pb (Ac) of 100ml0.67mol/L
23H
2O) in, flood and made the active acetate lead solution fully enter microsphere supported inside in 3 hours; Due to the amount of steeping fluid be according to carrier, the specific absorption of active ingredient is calculated selected, so described activity component impregnation liquid can disposable immersion described microsphere supported inside, can residual any plumbic acetate waste liquid.After above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 5 hours under 100 ℃, removes the moisture in carrier; Again load after drying there is afterwards the γ-Al of plumbic acetate
2O
3Carrier in 400 ℃ of lower calcination activations 10 hours, makes plumbic acetate decompose under aerobic conditions, and and then obtains γ-Al that load has the PbO active ingredient
2O
3Carrier.In said process, when the carrier after the steeping fluid dipping is carried out drying, preferred ambient is aerobic environment; Why will carry out drying and calcination activation to the carrier after the active component solution dipping under aerobic conditions, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, and this product covers collection at carrier surface, forms carbon distribution; Assurance just because of aerobic conditions, a small amount of C that pyrolytic decomposition can be obtained generates air release under aerobic environment, thereby the active spaced point that guarantees the active ingredient of carrier surface can fully contact with arsenic compound with sulphur compound and carry out absorption reaction, has guaranteed that further the desulfurization dearsenification of desulfurating and dearsenic agent is active.In addition, selecting maturing temperature is in order to realize better the Uniform Dispersion of active ingredient on carrier.
The ferric chloride Solution of 100ml0.18mol/L and the copper nitrate solution of 1000ml0.19mol/L are mixed, and fully stirring mixes it, then to the sodium carbonate solution of above-mentioned mixed solution and dripping 2000ml0.13mol/L, the pH value that guarantees solution is 7.2, thereby has obtained copper carbonate and iron carbonate throw out.Mentioned solution is carried out nature place ageing 0.5 hour, thereby guarantee that the throw out that reaction generates fully precipitates; Afterwards, use deionized water that above-mentioned throw out is washed and filters, the throw out after washing is separated; Above-mentioned washing times is with final Na
+Content in wash solution gets final product lower than 5ppm.Be 150m with above-mentioned copper carbonate and iron carbonate presoma and 2 1g after washing less than 80 orders, specific surface area
2/ g, pore volume are 10cm
3Microballoon γ-Al of/g
2O
3Carrier mixes, and kneading 0.5 hour.
γ-the Al that above-mentioned load is had the PbO active ingredient
2O
3Carrier and load have the γ-Al of copper carbonate and iron carbonate
2O
3Carrier carried out kneading 1 hour, after extruded moulding, with this forming composition under 105 ℃ dry 3 hours, under aerobic conditions, under 300 ℃, forming composition was after drying carried out calcination activation 10 hours afterwards, made the iron carbonate throw out be converted into martial ethiops Fe
21.333O
32, the copper carbonate throw out is converted into cupric oxide, thereby obtains containing active ingredient plumbous oxide 15wt%, martial ethiops Fe
21.333O
3230wt%, cupric oxide are 15wt%, γ-Al
2O
3The desulfurating and dearsenic agent of 40wt%.
Embodiment 7
Choose 80 orders, specific surface area is 100m
2/ g, pore volume are 10cm
3Microballoon γ-Al of/g
2O
3Carrier 19g puts into the plumbic acetate solution (Pb (Ac) of 1000ml 0.112mol/L
23H
2O) in, flood and made the active acetate lead solution fully enter microsphere supported inside in 3 hours; Due to the amount of steeping fluid be according to carrier, the specific absorption of active ingredient is calculated selected, so described activity component impregnation liquid can disposable immersion described microsphere supported inside, can residual any plumbic acetate waste liquid.After above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 5 hours under 100 ℃, removes the moisture in carrier; Again load after drying there is afterwards the γ-Al of plumbic acetate
2O
3Carrier in 400 ℃ of lower calcination activations 10 hours, makes plumbic acetate decompose under aerobic conditions, and and then obtains γ-Al that load has the PbO active ingredient
2O
3Carrier.In said process, when the carrier after the steeping fluid dipping is carried out drying, preferred ambient is aerobic environment; Why will carry out drying and calcination activation to the carrier after the active component solution dipping under aerobic conditions, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, and this product covers collection at carrier surface, forms carbon distribution; Assurance just because of aerobic conditions, a small amount of C that pyrolytic decomposition can be obtained generates air release under aerobic environment, thereby the active spaced point that guarantees the active ingredient of carrier surface can fully contact with arsenic compound with sulphur compound and carry out absorption reaction, has guaranteed that further the desulfurization dearsenification of desulfurating and dearsenic agent is active.In addition, selecting maturing temperature is in order to realize better the Uniform Dispersion of active ingredient on carrier.
The ferric chloride Solution of 1000ml0.3mol/L and the copper nitrate solution of 750ml0.5mol/L are mixed, and fully stirring mixes it, then to the sodium carbonate solution of above-mentioned mixed solution and dripping 5000ml0.137mol/L, the pH value that guarantees solution is 7.2, thereby has obtained copper carbonate and iron carbonate throw out.Mentioned solution is carried out nature place ageing 0.5 hour, thereby guarantee that the throw out that reaction generates fully precipitates; Afterwards, use deionized water that above-mentioned throw out is washed and filters, the throw out after washing is separated; Above-mentioned washing times is with final Na
+Content in wash solution gets final product lower than 5ppm.Be 100m with above-mentioned copper carbonate and iron carbonate presoma and 1g after washing less than 80 orders, specific surface area
2/ g, pore volume are 10cm
3Microballoon γ-Al of/g
2O
3Carrier mixes, and kneading 0.5 hour.
γ-the Al that above-mentioned load is had the PbO active ingredient
2O
3Carrier and load have the γ-Al of copper carbonate and iron carbonate
2O
3Carrier carried out kneading 1 hour, after extruded moulding, with this forming composition under 105 ℃ dry 3 hours, under aerobic conditions, under 300 ℃, forming composition was after drying carried out calcination activation 10 hours afterwards, made the iron carbonate throw out be converted into martial ethiops Fe
21.333O
32, the copper carbonate throw out is converted into cupric oxide, thereby obtains containing active ingredient plumbous oxide 25wt%, martial ethiops Fe
21.333O
3225wt%, cupric oxide are 30wt%, γ-Al
2O
3The desulfurating and dearsenic agent of 20wt%.
Embodiment 8
Choose 80 orders, specific surface area is 100m
2/ g, pore volume are 10cm
3Microballoon γ-Al of/g
2O
3Carrier 9g puts into the plumbic acetate solution (Pb (Ac) of 1000ml 0.112mol/L
23H
2O) in, flood and made the active acetate lead solution fully enter microsphere supported inside in 3 hours; Due to the amount of steeping fluid be according to carrier, the specific absorption of active ingredient is calculated selected, so described activity component impregnation liquid can disposable immersion described microsphere supported inside, can residual any plumbic acetate waste liquid.After above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 5 hours under 100 ℃, removes the moisture in carrier; Again load after drying there is afterwards the γ-Al of plumbic acetate
2O
3Carrier in 400 ℃ of lower calcination activations 10 hours, makes plumbic acetate decompose under aerobic conditions, and and then obtains γ-Al that load has the PbO active ingredient
2O
3Carrier.In said process, when the carrier after the steeping fluid dipping is carried out drying, preferred ambient is aerobic environment; Why will carry out drying and calcination activation to the carrier after the active component solution dipping under aerobic conditions, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, and this product covers collection at carrier surface, forms carbon distribution; Assurance just because of aerobic conditions, a small amount of C that pyrolytic decomposition can be obtained generates air release under aerobic environment, thereby the active spaced point that guarantees the active ingredient of carrier surface can fully contact with arsenic compound with sulphur compound and carry out absorption reaction, has guaranteed that further the desulfurization dearsenification of desulfurating and dearsenic agent is active.In addition, selecting maturing temperature is in order to realize better the Uniform Dispersion of active ingredient on carrier.
The ferric chloride Solution of 1000ml0.437mol/L and the copper nitrate solution of 1000ml0.375mol/L are mixed, and fully stirring mixes it, then to the sodium carbonate solution of above-mentioned mixed solution and dripping 4000ml0.2mol/L, the pH value that guarantees solution is 7.2, thereby has obtained copper carbonate and iron carbonate throw out.Mentioned solution is carried out nature place ageing 0.5 hour, thereby guarantee that the throw out that reaction generates fully precipitates; Afterwards, use deionized water that above-mentioned throw out is washed and filters, the throw out after washing is separated; Above-mentioned washing times is with final Na
+Content in wash solution gets final product lower than 5ppm.Be 100m with above-mentioned copper carbonate and iron carbonate presoma and 1g after washing less than 80 orders, specific surface area
2/ g, pore volume are 10cm
3Microballoon γ-Al of/g
2O
3Carrier mixes, and kneading 0.5 hour.
γ-the Al that above-mentioned load is had the PbO active ingredient
2O
3Carrier and load have the γ-Al of copper carbonate and iron carbonate
2O
3Carrier carried out kneading 1 hour, after extruded moulding, with this forming composition under 105 ℃ dry 3 hours, under aerobic conditions, under 300 ℃, forming composition was after drying carried out calcination activation 10 hours afterwards, made the iron carbonate throw out be converted into martial ethiops Fe
21.333O
32, the copper carbonate throw out is converted into cupric oxide, thereby obtains containing active ingredient plumbous oxide 25wt%, martial ethiops Fe
21.333O
3235wt%, cupric oxide are 30wt%, γ-Al
2O
3The desulfurating and dearsenic agent of 10wt%.
The activity rating example
The desulfurating and dearsenic agent that above-described embodiment is prepared is ground into 20～40 purpose particles, and filling it into internal diameter is in the 2ml clean-up bed of 8mm.Be 2000h in normal temperature, normal pressure, air speed
-1Condition under,, by this clean-up bed desulfurization, the dearsenification effect of this desulfurating and dearsenic agent are estimated with the nitrogen that contains different concns sulphur, arsenic compound impurity, acquired results is as follows:
This shows, the desulfurization of the desulfurating and dearsenic agent that the present invention prepares, dearsenification effect are very remarkable, and the Sulfur capacity arsenic of the desulfurating and dearsenic agent for preparing obviously holds up to more than 15wt%; Its desulfurization arsenic-removing rate is also very high, and up to more than 99%, due to present technical limitation, the technology acuracy of instrument can't have been determined 99% later numerical value of this desulfurization arsenic-removing rate.Described desulfurization arsenic-removing rate refers to the per-cent of the amount of the amount of the sulphur compound that removes and former sulfide.As seen, use desulfurating and dearsenic agent of the present invention to have higher desulfurization dearsenification activity.
Martial ethiops Fe described in the present invention
21.333O
32Be the homemade product of applicant, although this material is abnormal iron cpd, this product can find out clearly that in XRD standard card it is a kind of in ferriferous oxide equally; Described this martial ethiops Fe
21.333O
32XRD spectra corresponding to XRD standard card numerical value referring to accompanying drawing 1.
Although the present invention elaborates it by embodiment; but; those skilled in the art should be understood that any form that does not exceed the claim protection domain made on this basis and the variation of details, all belong to invention which is intended to be protected.
Claims (19)
1. a desulfurating and dearsenic agent, be made of carrier and active ingredient, it is characterized in that, described active ingredient is plumbous oxide 0.1～40wt%, martial ethiops Fe
21.333O
320.1～60wt%, cupric oxide are 0.1～40wt%; Described carrier accounts for 10～80wt% of desulfurating and dearsenic agent gross weight;
The preparation of described desulfurating and dearsenic agent comprises the steps:
(1) adopt " doing " to soak method, carrier impregnation in active ingredient lead salt solution, was flooded 0.5～3 hour;
(2) will flood carrier after lead salt, 100～120 ℃ of dryings 1～5 hour; The carrier that after drying load is had a lead salt is equally under aerobic conditions, in 400～900 ℃ of lower calcination activations 3～10 hours;
(3) iron salt solutions of solubility and copper salt solution are mixed, and fully stir it is mixed, then to above-mentioned mixed solution and dripping sodium carbonate or sodium hydroxide solution, the pH value to 7.2 of regulator solution～7.6 generate the throw out of iron, copper simultaneously;
(4) throw out that obtains in step (3) is carried out nature and place ageing, be 0.5 ~ 8 hour storage period; Afterwards the throw out presoma is washed and filters;
(5) product that step (4) is obtained and carrier mix, and fully kneading is 0.5 ~ 1 hour;
(6) product that obtains in the product that obtains in described step (2) and step (5) was carried out kneading 1～3 hour, extrusion or roller forming also carry out drying, afterwards under aerobic conditions, in 300～900 ℃ of lower calcination activations 3～10 hours, namely obtain desulfurating and dearsenic agent.
2. desulfurating and dearsenic agent according to claim 1, is characterized in that, in described active ingredient, plumbous oxide content is 0.1～20wt%.
3. desulfurating and dearsenic agent according to claim 2, is characterized in that, in described active ingredient, plumbous oxide content is 5～20wt%.
4. desulfurating and dearsenic agent according to claim 1, is characterized in that, martial ethiops Fe in described active ingredient
21.333O
32Content is 0.1～40wt%.
5. desulfurating and dearsenic agent according to claim 4, is characterized in that, martial ethiops Fe in described active ingredient
21.333O
32Content is 20～40wt%.
6. desulfurating and dearsenic agent according to claim 1, is characterized in that, in described active ingredient, cupric oxide content is 0.1～20wt%.
7. desulfurating and dearsenic agent according to claim 6, is characterized in that, in described active ingredient, cupric oxide content is 0.1～10wt%.
8. desulfurating and dearsenic agent according to claim 1, is characterized in that, described vector contg is 10～60wt%.
9. desulfurating and dearsenic agent according to claim 8, is characterized in that, described vector contg is 20～40wt%.
10. according to claim 1,8,9 arbitrary described desulfurating and dearsenic agents, it is characterized in that, described carrier is γ-Al
2O
3
11. according to claim 1 or 8 or 9 described desulfurating and dearsenic agents is characterized in that, the specific surface area of described carrier is 20～350m
2/ g, pore volume are 0.1～20cm
3/ g.
12. desulfurating and dearsenic agent according to claim 10 is characterized in that, the specific surface area of described carrier is 60～300m
2/ g, pore volume are 0.3～1.2cm
3/ g.
13. according to claim 1-9 arbitrary described desulfurating and dearsenic agents is characterized in that described lead salt is plumbic acetate.
14. according to claim 1-9 arbitrary described desulfurating and dearsenic agents is characterized in that, carry out drying in described step (2) under aerobic conditions.
15. according to claim 1-9 arbitrary described desulfurating and dearsenic agents is characterized in that the maturing temperature in described step (2) is 500～650 ℃, soak time is 5～8 hours.
16. according to claim 1-9 arbitrary described desulfurating and dearsenic agents is characterized in that the pH value in described step (3) is 7.4.
17. according to claim 1-9 arbitrary described desulfurating and dearsenic agents is characterized in that, are warming up to 60～85 ℃ in described step (3) when regulating the pH value and react.
18. according to claim 1-9 arbitrary described desulfurating and dearsenic agents is characterized in that, in described step (6), drying temperature is 105～110 ℃, and be 1～3 hour time of drying.
19. according to claim 1-9 arbitrary described desulfurating and dearsenic agents is characterized in that the maturing temperature in described step (6) is 350～650 ℃, soak time is 4～8 hours.
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| CN104548867B (en) * | 2013-10-28 | 2017-02-15 | 中国石油化工股份有限公司 | Method for adsorbing sulphur and arsenic |
| CN104549128B (en) * | 2013-10-28 | 2017-02-15 | 中国石油化工股份有限公司 | Sulfur-arsenic purifying agent and application thereof |
| CN105582879B (en) * | 2014-10-24 | 2018-05-11 | 中国石油化工股份有限公司 | Sulphur arsenic cleanser and preparation method thereof |
| BR102016022626B1 (en) * | 2016-09-29 | 2021-06-01 | Petróleo Brasileiro S.A. - Petrobras | SIMULTANEOUS REMOVAL PROCESS OF ARSENIC AND SULFUR FROM HYDROCARBON CHAINS |
| 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 |
| CN114934170B (en) * | 2022-05-23 | 2024-04-19 | 江西理工大学 | Method for separating arsenic and antimony from copper electrolysis black copper sludge and recovering copper |
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| CN1580196A (en) * | 2003-08-07 | 2005-02-16 | 上海化工研究院 | Dearsenicating agent for removing high boiling point arsonium compound in liquid-state petroleum hydrocarbon at low temperature and normal temperature |
| CN1667091A (en) * | 2004-03-12 | 2005-09-14 | 上海化工研究院 | Normal temperature dearsenization agent for liquid petroleum hydrocarbon |
| CN1671825A (en) * | 2002-07-22 | 2005-09-21 | 出光兴产株式会社 | Method for desulfurizing liquid hydrocarbons and method for producing hydrogen for fuel cells |
| CN1923966A (en) * | 2005-09-02 | 2007-03-07 | 上海化工研究院 | Liquid state petroleum hydrocarbon normal temperature dearsenicating agent and preparation method thereof |
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|---|---|---|---|---|
| CN1671825A (en) * | 2002-07-22 | 2005-09-21 | 出光兴产株式会社 | Method for desulfurizing liquid hydrocarbons and method for producing hydrogen for fuel cells |
| CN1580196A (en) * | 2003-08-07 | 2005-02-16 | 上海化工研究院 | Dearsenicating agent for removing high boiling point arsonium compound in liquid-state petroleum hydrocarbon at low temperature and normal temperature |
| CN1667091A (en) * | 2004-03-12 | 2005-09-14 | 上海化工研究院 | Normal temperature dearsenization agent for liquid petroleum hydrocarbon |
| CN1923966A (en) * | 2005-09-02 | 2007-03-07 | 上海化工研究院 | Liquid state petroleum hydrocarbon normal temperature dearsenicating agent and preparation method thereof |
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