CN101591554A - A kind of normal temperature composite desulfurating and dearsenic agent and preparation method thereof - Google Patents
A kind of normal temperature composite desulfurating and dearsenic agent and preparation method thereof Download PDFInfo
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- CN101591554A CN101591554A CNA2008101140954A CN200810114095A CN101591554A CN 101591554 A CN101591554 A CN 101591554A CN A2008101140954 A CNA2008101140954 A CN A2008101140954A CN 200810114095 A CN200810114095 A CN 200810114095A CN 101591554 A CN101591554 A CN 101591554A
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Abstract
The present invention relates to a kind of desulfurating and dearsenic agent, this desulfurating and dearsenic agent is made of carrier and active ingredient, wherein said carrier can be single carrier, also can be that two or more carrier constitutes, and described carrier accounts for 10～80wt% of desulfurating and dearsenic agent gross weight; Described active ingredient is plumbous oxide 0.1～40wt%, martial ethiops Fe
21.333O
320.1～60wt%, cupric oxide are 0.1～40wt%.The present invention also further discloses the preparation method of this desulfurating and dearsenic agent.The desulfurating and dearsenic agent that uses this method to prepare has high Sulfur capacity and arsenic holds, and its desulfurization arsenic-removing rate can be up to more 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 multiple metallic impurity and nonmetallic impurity in the oil, as iron, nickel, vanadium, copper, lead, sulphur, nitrogen, arsenic etc.Oil is being processed in the refining process, most of impurity can removed basically, making foreign matter content be reduced to certain level, but the trace impurity that remains in oil inside, processing back still influences grade of oil inevitably.For example, after heavier petroleum fraction carried out cracking (catalytic cracking, catalytic pyrolysis, visbreaking and coking) and handle, 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, also may be 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 arsenical above-mentioned lighter hydrocarbons are underproof raw materials; If will contain sulphur or arsenic such as light-end products such as petroleum naphthas as the cracking of ethylene raw material, the impurity arsenic of this light-end products inside not only can influence the coke cleaning period of pyrolyzer and the yield of ethene, and may cause the poisoning of hydrogenation catalyst in the follow-up hydrogenation device and the poisoning of poly-unit olefin polymerization catalysis, directly influence quality product; Similarly, sulfur impurity also can exert an influence to the activity of hydrogenation catalyst.So,, must carry out desulfurization and dearsenification pre-treatment to above-mentioned lighter hydrocarbons, otherwise it can't directly apply in the follow-up Chemical Manufacture for fear of the problems referred to above.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 then is desulfurating and dearsenic agent (also being desulfurization dearsenification scavenging agent).Wherein, desulfurating and dearsenic agent can play by reaction sulfur impurity contained in the lighter hydrocarbons and arsenic are removed, and, make desulfurating and dearsenic agent regenerate, so in Chemical Manufacture, often select for use the dearsenification desulfurizing decontaminating agent to carry out desulfurization dearsenification pre-treatment by the subsequent regeneration program.
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 the nitrate of copper, iron, manganese, nickel, five kinds of elements of silver or in muriate or vitriol or sulfide or the oxalate compound one or more active ingredient constituted.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 also heating, behind the transpiring moisture, obtains active main the branch and the mixture of carrier; Add shaping structures agent thorough mixing afterwards, also dry after the extrusion moulding, and then under 200～700 ℃, heat-treated 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 method for preparing obtains is 16.47～24.64gAs/Kg, also is that its arsenic capacity only is 1.647～2.464wt%.From its reaction principle, it is in the process of preparation dearsenic agent, and so the main still dipping method that uses is its inevitable problem that causes the transition metal solution environmental pollution owing to steeping fluid is excessive of having brought inevitably.
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 that carries above-mentioned active ingredient constitutes.This dearsenic agent equally can scalable character liquid condition petroleum hydrocarbon, and also all fine to the adaptability of moisture in the 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 same easy pollution of transition metal solution to environment that cause owing to steeping fluid is excessive of this method.
Though 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.
U.S. Pat 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 the hydrocarbon gas.For this preparation of adsorbent, it can use coprecipitation method, decomposition method, pickling process and mechanical mixing, preferably uses coprecipitation method or decomposition method.
From above-mentioned prior art document as can be seen, in normally used dearsenification sweetening agent, mostly adopt be with active constituent loading on carrier so that realize its desulfurization dearsenification pre-treatment to lighter hydrocarbons; Wherein, carrier comprises molecular sieve, titanium dioxide, silicon-dioxide, aluminum oxide etc. mostly, the compound of 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 big more options iron in its active compound
2O
3For disclosed desulfurating and dearsenic agent in the present prior art, also there is a kind of undesirable state on the performance in it, promptly 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 adopt mostly for the preparation of above-mentioned desulfurating and dearsenic agent all is single preparation method, because the deficiency that various preparation methods have its method itself to exist, more or less product characteristics is produced to a certain degree influence, so prepare desulfurating and dearsenic agent and will stabilize and increase product performance to a great extent if can effectively the preparation method be coupled.
Summary of the invention
Technical problem to be solved by this invention is that the Sulfur capacity and the arsenic appearance of desulfurating and dearsenic agent in the prior art is lower, and owing to use 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, plumbous oxide content is 0.1～20wt% in the preferred described active ingredient, and most preferably plumbous oxide content is 5～20wt%; Martial ethiops Fe in the preferred described active ingredient
21.333O
32Content is 0.1～40wt%, most preferably martial ethiops Fe
21.333O
32Content is 20～40wt%; Cupric oxide content is 0.1～20wt% in the preferred described active ingredient, and most preferably cupric oxide content is 0.1～10wt%.The content of carrier is 10～60wt% in the preferred described desulfurating and dearsenic agent, 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 the 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 also can be 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) adopts " doing " to soak method, carrier impregnation in active ingredient lead salt solution, was flooded 0.5～3 hour;
(2) will flood carrier behind the lead salt, 100～120 ℃ of dryings 1～5 hour; With the carrier behind the load lead salt after drying equally under aerobic conditions, in 400～900 ℃ of following 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 yellow soda ash 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 the 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 mix and pinch 0.5～1 hour;
(6) product that obtains in the product that obtains in the described step (2) and the step (5) is mixed pinch 1～3 hour, extrusion or roller forming also carry out drying, afterwards under aerobic conditions,, promptly obtain desulfurating and dearsenic agent in 300～900 ℃ of following calcination activations 3～10 hours.
Wherein, described lead salt is a plumbic acetate.Under aerobic conditions, carry out drying in the described step (2); In roasting process, maturing temperature is 500～650 ℃, and soak time is 5～8 hours.PH value in the described step (3) is 7.4; Being warming up to 60～85 ℃ when regulating pH value reacts.Drying temperature is 105～110 ℃ in the described step (6), 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 uses " doing " to soak the follow-up in addition calcination procedure of method and has 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 of calculating good selected carrier, determining can be by flooding the disposable amount that is carried on the active ingredient on the 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 for use, realizes the coprecipitation of copper, iron in the desulfurating and dearsenic agent active ingredient of the present invention, thus the uniform mixing of copper throw out and iron precipitate; On this basis, in mixed uniformly copper throw out and iron precipitate, add an amount of carrier,, make that above-mentioned copper throw out and iron precipitate can uniform loadings and be scattered on the carrier by kneading method.At last, adopt kneading method once more, 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, mix and pinch 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 helps obtaining 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 the generation of waste liquid on the one hand, also reduced the burden of washing in the preparation procedure on the other hand, improved the preparation efficiency of desulfurating and dearsenic agent.
The present invention has advantage 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 the 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 dry immersion, coprecipitation method and kneading method coupled preparation method to prepare desulfurating and dearsenic agent of the present invention; Wherein, use dry immersion, select the water regain of the carrier of use can control the amount of steeping fluid effectively, guarantee that steeping fluid fully enters carrier inside and do not have remaining steeping fluid residual, reduced of the pollution of the residual waste liquid of steeping fluid environment by calculating; Use coprecipitation method can obtain the coprecipitation thing of active element in the active ingredient, and the throw out ratio of mixture is more even, will it and carrier is fully mixed pinches, 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 that the sedimentary carrier thorough mixing of active element is arranged through load with above-mentioned, thereby guarantee the uniform loading of uniform active ingredient on carrier better, 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; Since 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 the described microsphere supported inside of disposable immersion, can residual any plumbic acetate waste liquid.After treating that above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 5 hours under 100 ℃, removes the moisture in the carrier; γ-the Al that again load is after drying had plumbic acetate afterwards
2O
3Carrier in 400 ℃ of following 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, be aerobic environment to preferred ambient when the steeping fluid soaked carrier is carried out drying; Why will be to carrying out drying and calcination activation under aerobic conditions through the active component solution soaked carrier, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, 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 gas 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 further guaranteed the desulfurization dearsenification activity of desulfurating and dearsenic agent.In addition, selecting maturing temperature is in order to realize the homodisperse of active ingredient on carrier better.
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.Above-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, will separate through the throw out after the washing; Above-mentioned washing times is with final Na
+Content in wash solution is lower than 5ppm and gets final product.Is 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 mixes and pinched 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 mixes pinches 1 hour, after the extruded moulding, this forming composition is descended dry 3 hours at 105 ℃, under aerobic conditions, under 300 ℃ forming composition is after drying carried out calcination activation 10 hours afterwards, makes 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; Since 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 the described microsphere supported inside of disposable immersion, can residual any plumbic acetate waste liquid.After treating that above-mentioned steeping fluid immerses carrier fully, carrier is taken out, under aerobic conditions,, remove the moisture in the carrier in 120 ℃ times dry 1 hour; γ-the Al that again load is after drying had plumbic acetate afterwards
2O
3Carrier in 650 ℃ of following 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, be aerobic environment to preferred ambient when the steeping fluid soaked carrier is carried out drying; Why will be to carrying out drying and calcination activation under aerobic conditions through the active component solution soaked carrier, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, 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 gas 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 further guaranteed the desulfurization dearsenification activity of desulfurating and dearsenic agent.
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, will separate through the throw out after the washing; Above-mentioned washing times is with final Na
+Content in wash solution is lower than 5ppm and gets final product.With above-mentioned copper carbonate and iron protocarbonate presoma and 14.94g 60 orders, specific surface area after washing is 20m
2/ g, pore volume are 0.1cm
3Microballoon γ-Al of/g
2O
3Carrier mixes, and mixes and pinched 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 mixes pinches 3 hours, after the extruded moulding, this forming composition is descended dry 1 hour at 110 ℃, under aerobic conditions, under 650 ℃ forming composition is after drying carried out calcination activation 4 hours afterwards, makes 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 the 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; Since 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 the described microsphere supported inside of disposable immersion, can residual any plumbic acetate waste liquid.After treating that above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 2.5 hours under 110 ℃, removes the moisture in the carrier; The gac that load that again will be after drying afterwards has plumbic acetate in 500 ℃ of following 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, be aerobic environment to preferred ambient when the steeping fluid soaked carrier is carried out drying; Why will be to carrying out drying and calcination activation under aerobic conditions through the active component solution soaked carrier, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, 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 gas 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 further guaranteed the desulfurization dearsenification activity of desulfurating and dearsenic agent.
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, thereby generate copper carbonate and iron carbonate throw out to 60 ℃.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, will separate, can get copper carbonate and iron carbonate through the throw out after the washing; Above-mentioned washing times is with final Na
+Content in wash solution is lower than 5ppm and gets final product.With above-mentioned copper carbonate and iron carbonate presoma and 47g 120 orders, specific surface area after washing is 350m
2/ g, pore volume are 20cm
3The gac of/g mixes, and mixes and pinched 0.6 hour.Heating in 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 causes reactant or product easily.
There are the gac of PbO active ingredient and load to have the gac of copper carbonate and iron carbonate to mix above-mentioned load and pinch 1.5 hours, after the roller forming, this forming composition is following dry 2 hours at 108 ℃, 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; Since 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 the described microsphere supported inside of disposable immersion, can residual any plumbic acetate waste liquid.After treating that above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 2.5 hours under 110 ℃, removes the moisture in the carrier; γ-the Al that again load is after drying had plumbic acetate afterwards
2O
3Under aerobic conditions, in 500 ℃ of following 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, be aerobic environment to preferred ambient when the steeping fluid soaked carrier is carried out drying; Why will be to carrying out drying and calcination activation under aerobic conditions through the active component solution soaked carrier, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, 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 gas 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 further guaranteed the desulfurization dearsenification activity of desulfurating and dearsenic agent.
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, will separate, obtain copper hydroxide and bulky ferric hydroxide precipitate through the throw out after the washing; Above-mentioned washing times is with final Na
+Content in wash solution is lower than 5ppm and gets final product.With above-mentioned copper hydroxide and bulky ferric hydroxide precipitate and 65g 120 orders, specific surface area after washing is 350m
2/ g, pore volume are 20cm
3The gac of/g mixes, and mixes and pinched 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 mix to pinch 1.5 hours, after the roller forming, this forming composition is following dry 2 hours at 108 ℃, 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; Since 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 the described microsphere supported inside of disposable immersion, can residual any plumbic acetate waste liquid.After treating that above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 2.5 hours under 110 ℃, removes the moisture in the carrier; The gac that load that again will be after drying afterwards has plumbic acetate in 500 ℃ of following 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, be aerobic environment to preferred ambient when the steeping fluid soaked carrier is carried out drying; Why will be to carrying out drying and calcination activation under aerobic conditions through the active component solution soaked carrier, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, 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 gas 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 further guaranteed the desulfurization dearsenification activity of desulfurating and dearsenic agent.
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, thereby generate copper carbonate and iron carbonate throw out to 60 ℃.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, will separate, can get copper carbonate and iron carbonate through the throw out after the washing; Above-mentioned washing times is with final Na
+Content in wash solution is lower than 5ppm and gets final product.With above-mentioned copper carbonate and iron carbonate throw out and 56.4g 120 orders, specific surface area after washing is 200m
2/ g, pore volume are 20cm
3The gac of/g mixes, and mixes and pinched 0.6 hour.Heating in 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 causes reactant or product easily.
There are the gac of PbO active ingredient and load to have the gac of copper carbonate and iron carbonate to mix above-mentioned load and pinch 1.5 hours, after the roller forming, this forming composition is following dry 2 hours at 108 ℃, 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; Since 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 the described microsphere supported inside of disposable immersion, can residual any plumbic acetate waste liquid.After treating that above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 5 hours under 100 ℃, removes the moisture in the carrier; γ-the Al that again load is after drying had plumbic acetate afterwards
2O
3Carrier in 400 ℃ of following 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, be aerobic environment to preferred ambient when the steeping fluid soaked carrier is carried out drying; Why will be to carrying out drying and calcination activation under aerobic conditions through the active component solution soaked carrier, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, 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 gas 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 further guaranteed the desulfurization dearsenification activity of desulfurating and dearsenic agent.In addition, selecting maturing temperature is in order to realize the homodisperse of active ingredient on carrier better.
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.Above-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, will separate through the throw out after the washing; Above-mentioned washing times is with final Na
+Content in wash solution is lower than 5ppm and gets final product.Is 150m with above-mentioned copper carbonate and iron carbonate presoma and 21g after washing less than 80 orders, specific surface area
2/ g, pore volume are 10cm
3Microballoon γ-Al of/g
2O
3Carrier mixes, and mixes and pinched 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 mixes pinches 1 hour, after the extruded moulding, this forming composition is descended dry 3 hours at 105 ℃, under aerobic conditions, under 300 ℃ forming composition is after drying carried out calcination activation 10 hours afterwards, makes 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; Since 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 the described microsphere supported inside of disposable immersion, can residual any plumbic acetate waste liquid.After treating that above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 5 hours under 100 ℃, removes the moisture in the carrier; γ-the Al that again load is after drying had plumbic acetate afterwards
2O
3Carrier in 400 ℃ of following 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, be aerobic environment to preferred ambient when the steeping fluid soaked carrier is carried out drying; Why will be to carrying out drying and calcination activation under aerobic conditions through the active component solution soaked carrier, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, 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 gas 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 further guaranteed the desulfurization dearsenification activity of desulfurating and dearsenic agent.In addition, selecting maturing temperature is in order to realize the homodisperse of active ingredient on carrier better.
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.Above-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, will separate through the throw out after the washing; Above-mentioned washing times is with final Na
+Content in wash solution is lower than 5ppm and gets final product.Is 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 mixes and pinched 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 mixes pinches 1 hour, after the extruded moulding, this forming composition is descended dry 3 hours at 105 ℃, under aerobic conditions, under 300 ℃ forming composition is after drying carried out calcination activation 10 hours afterwards, makes 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; Since 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 the described microsphere supported inside of disposable immersion, can residual any plumbic acetate waste liquid.After treating that above-mentioned steeping fluid immerses carrier fully, carrier is taken out, drying is 5 hours under 100 ℃, removes the moisture in the carrier; γ-the Al that again load is after drying had plumbic acetate afterwards
2O
3Carrier in 400 ℃ of following 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, be aerobic environment to preferred ambient when the steeping fluid soaked carrier is carried out drying; Why will be to carrying out drying and calcination activation under aerobic conditions through the active component solution soaked carrier, its purpose is to prevent that plumbic acetate from high temperature decomposing generation C, 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 gas 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 further guaranteed the desulfurization dearsenification activity of desulfurating and dearsenic agent.In addition, selecting maturing temperature is in order to realize the homodisperse of active ingredient on carrier better.
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.Above-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, will separate through the throw out after the washing; Above-mentioned washing times is with final Na
+Content in wash solution is lower than 5ppm and gets final product.Is 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 mixes and pinched 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 mixes pinches 1 hour, after the extruded moulding, this forming composition is descended dry 3 hours at 105 ℃, under aerobic conditions, under 300 ℃ forming composition is after drying carried out calcination activation 10 hours afterwards, makes 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 the foregoing description is prepared is ground into 20～40 purpose particles, and filling it into internal diameter is in the 2ml clean-up bed of 8mm.In normal temperature, normal pressure, air speed is 2000h
-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, the gained result is as follows:
This shows that 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 the 15wt%; Its desulfurization arsenic-removing rate is also very high, and up to more than 99%, because 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 is meant 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, though this material is abnormal iron cpd, this product can find out clearly that in XRD standard card it is a kind of in the ferriferous oxide equally; Described this martial ethiops Fe
21.333O
32The XRD spectra of XRD standard card numerical value correspondence referring to accompanying drawing 1.
Though the present invention elaborates it by embodiment; but; the any form that does not exceed the claim protection domain that those skilled in the art should be understood that on this basis to be made and the variation of details all belong to invention which is intended to be protected.
Claims (20)
1. a desulfurating and dearsenic agent is 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.
2. desulfurating and dearsenic agent according to claim 1 is characterized in that, plumbous oxide content is 0.1～20wt% in the described active ingredient.
3. desulfurating and dearsenic agent according to claim 2 is characterized in that, plumbous oxide content is 5～20wt% in the described active ingredient.
4. desulfurating and dearsenic agent according to claim 1 is characterized in that, martial ethiops Fe in the 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 the described active ingredient
21.333O
32Content is 20～40wt%.
6. desulfurating and dearsenic agent according to claim 1 is characterized in that, cupric oxide content is 0.1～20wt% in the described active ingredient.
7. desulfurating and dearsenic agent according to claim 6 is characterized in that, cupric oxide content is 0.1～10wt% in the described active ingredient.
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., it is characterized in that the specific surface area of described carrier is 20～350m according to claim 1 or 8 or 9 described desulfurating and dearsenic agents
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. the preparation method of a desulfurating and dearsenic agent comprises the steps:
(1) adopts " doing " to soak method, carrier impregnation in active ingredient lead salt solution, was flooded 0.5～3 hour;
(2) will flood carrier behind the 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 following 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 yellow soda ash 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 the 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 mix and pinch 0.5～1 hour;
(6) product that obtains in the product that obtains in the described step (2) and the step (5) is mixed pinch 1～3 hour, extrusion or roller forming also carry out drying, afterwards under aerobic conditions,, promptly obtain desulfurating and dearsenic agent in 300～900 ℃ of following calcination activations 3～10 hours.
14. preparation method according to claim 13 is characterized in that, described lead salt is a plumbic acetate.
15. preparation method according to claim 13 is characterized in that, carries out drying in the described step (2) under aerobic conditions.
16. preparation method according to claim 13 is characterized in that, the maturing temperature in the described step (2) is 500～650 ℃, and soak time is 5～8 hours.
17. preparation method according to claim 13 is characterized in that, the pH value in the described step (3) is 7.4.
18. preparation method according to claim 13 is characterized in that, is warming up to 60～85 ℃ in the described step (3) when regulating pH value and reacts.
19. preparation method according to claim 13 is characterized in that, drying temperature is 105～110 ℃ in the described step (6), and be 1～3 hour time of drying.
20. preparation method according to claim 13 is characterized in that, the maturing temperature in the described step (6) is 350～650 ℃, and soak time is 4～8 hours.
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|---|---|---|---|
| CN200810114095.4A CN101591554B (en) | 2008-05-30 | 2008-05-30 | Normal temperature compound desulfuration and dearsenization agent and preparation method thereof |
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|---|---|---|---|
| CN200810114095.4A CN101591554B (en) | 2008-05-30 | 2008-05-30 | Normal temperature compound desulfuration and dearsenization agent and preparation method thereof |
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| CN104549128A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Sulfur-arsenic purifying agent and application thereof |
| CN105582879A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Purifying agent for sulfur and arsenic and preparation method thereof |
| 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 |
| CN107880923A (en) * | 2016-09-29 | 2018-04-06 | 巴西石油公司 | Method for removing arsenic removal and sulphur simultaneously from hydrocarbon stream |
| CN113999085A (en) * | 2021-12-02 | 2022-02-01 | 西安元创化工科技股份有限公司 | Hydrocarbon raw material deep purification method |
| CN114934170A (en) * | 2022-05-23 | 2022-08-23 | 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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| 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 |
| CN114934170A (en) * | 2022-05-23 | 2022-08-23 | 江西理工大学 | Method for separating arsenic and antimony from copper electrolysis black copper sludge and recovering copper |
| 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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|---|---|
| CN101591554B (en) | 2013-05-08 |
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