CN87101795A - Use water-soluble, polymeric chelate and oxidation state polyvalent metal composition from fluid, to remove the method and the said composition of hydrogen sulfide - Google Patents

Abstract

The present invention relates to a kind of circulation continuation method and composition that from various acid gas streams, removes hydrogen sulfide.This acid gas stream contacts with the aqueous solution of the composition that contains water soluble organic substance inner complex and oxidation state polyvalent metal such as Fe (III).Sulphur in the hydrogen sulfide is converted into elementary sulfur, and the iron rule in the polymeric chelates is reduced.This method comprises and removes elementary sulfur and remove the inexpensive method (preferably using super-filtering method or permeating method) that water and excessive low molecular weight substance such as molecular weight are lower than 500 material, and the regeneration of reactive polyvalent metal and recycling.

Description

Use water-soluble, polymeric chelate and oxidation state polyvalent metal composition from fluid, to remove the method and the said composition of hydrogen sulfide

The present invention relates to a kind of compositions-treated of a kind of usefulness, to contain obnoxious flavour be hydrogen sulfide (H ₂S) fluidic method, said composition contain water-soluble, polymeric chelate and with H ₂The S oxidation, soon sulphur wherein is oxidized to the polyvalent metal of element sulphur.Use such as methods such as dialysis or ultra-filtration are isolated elementary sulfur and the polymeric chelates of the as-reduced metal in the aqueous solution are concentrated.Make polyvalent metal chelates oxidation and repeated use then.More particularly, the present invention relates to use Fe ^{+ 3}The aqueous solution of the water-soluble, polymeric chelate of the iron of valence state removes H from air-flow ₂S, use super-filtering method or dialysis method separating element sulfenyl, concentrate the ferrous iron inner complex the aqueous solution, make Fe ^{+ 2}Be oxidized to Fe ^{+ 3}And polymeric chelates is reused.The present invention also relates to be used for the composition of this method.

Narrated in the United States Patent (USP) 4123506 and 4202864 and can contain H by making ₂The underground hot-fluid metallizing thing contact of S forms insoluble metallic sulfide makes fluid purification.The deposition cost of metallic sulfide thereafter is expensive and time-consuming.

United States Patent (USP) 4414817 and 4468929 discloses through making the aqueous solution condensation of underground hot-fluid and monomer ferric chelate such as N-HEDTA, handles the method for underground hot-fluid.Hydrogen sulfide is converted into elementary sulfur, and ferric chelate is reduced to the ferrous iron inner complex.Ferric iron monomer inner complex is oxidized to the monomer ferric chelate and reuses.

United States Patent (USP) 4400368 discloses a kind of hydrogen sulfide in the various air-flows and circulation means of carbonic acid gas of removing." acid gas " air-flow that contains these sour gas is contacted with the monomer ligand of the polyvalent metal of regulation or the aqueous solution of inner complex or their mixture, and hydrogen sulfide is oxidized to elementary sulfur, and reactive metal monomer inner complex is reduced.This method comprises that sulphur removes the regeneration with the reactive metal inner complex.And the unexposed measure that removes low molecular weight product or water of this method.

United States Patent (USP) 4189462 and 4218342 discloses a kind of composition that is used for the oxidation-reduction reaction process, and said composition contains a kind of monomeric solubility trivalent iron salt, can make the hydrogen sulfide catalyzed oxidation.The method of the organic polymer inner complex of the unexposed use iron of this document.

United States Patent (USP) 4518745 discloses the metallo-chelate of some water solubility copolymers.This multipolymer can be used as dyeing auxiliary and leather composite tanning agent.

United States Patent (USP) 4518577 discloses and has a kind ofly removed H from the acid gas air-flow ₂The method of S.The aqueous solution with the monomer organic acid oxidation state polyvalent metal chelates of stipulating makes H ₂The S oxidation, and from the regulation the organic extraction agent solution with sulphur content from and regeneration.

United States Patent (USP) 4518576 discloses a kind of circulation means that removes hydrogen sulfide from various air-flows.Monomer inner complex and phosphate crystal properties-correcting agent with iron (III) contact with the acid gas air-flow with the aqueous solution of thiosulfate ion mixture, make H ₂S is oxidized to elementary sulfur, and makes the reduction of reactant thiosulphate.This method comprises regeneration and the circulation that removes sulphur and reactant.

United States Patent (USP) 4332781 discloses a kind of substep removes hydrogen sulfide and carbon oxysulfide from air-flow method, and the feature of this method is in the aqueous solution or suspension hydrogen sulfide to be changed into sulphur.Reactant comprises the polyvalent metal that connects with monomer inner complex key.

United States Patent (USP) 4423158 discloses the method for group introducing such as the polymkeric substance such as polystyrene that will form inner complex.Can obtain a kind of divalence or polyvalent metal ion sorbent material that can be used for ion-exchange chromatography.Not mentioned use water-soluble, polymeric chelate of this patent or the method that is used for from fluid stream, removing H S, reclaims polymeric chelates and active metallic ion of the present invention.

Therefore, the monomer organic chelate of more existing use iron (III) is handled exhaust flow or the acid gas for the treatment of process generation or the technology of sour water of underground hot-fluid well.The problem that these treatment processs are brought is exactly generally to be difficult to from current the monomer organic chelate of iron (II) or iron (III) and cumulative excessive water, product and by product in treating processes be separated effectively, and costs a lot of money.When dividing dried up and low molecular weight substance, lost the very expensive iron of a part of price-monomer organic chelate, can't reclaim.Thereby wish that very a kind of method can be arranged, can be from containing H originally ₂Isolate very expensive organic iron (III) of price or iron (II) polymeric chelates at an easy rate in the waste water stream of S, and can circulate repeatedly.The invention provides a kind of so improved method and the composition that is used for this method.

The present invention relates to a kind of composition, it comprises

(1) a kind of water-soluble organic polymer inner complex, wherein the weight-average molecular weight of inner complex is between 1000 to 500000, and the component of polymer of inner complex is:

The X in each polymer unit wherein ₁Can at random be-H or R-, R-be-CH ₂COOH ,-CH ₂CH ₂COOH ,-CH ₂-P(=0) (OH) ₂Or

R wherein ₁And R ₂Can be arbitrarily-CH ₃,-SO ₃H ,-Cl ,-H or-COOH, n is the integer between 5 to 20000;

The X in each polymer unit wherein ₂Be-H ,-CH ₂CH(OH) CH ₂OH ,-CH ₂CH(OH) CH ₂Cl or

R wherein ₃, R ₄And R ₅Can be arbitrarily previously defined R, P be 5 to 20000 integer; Q is 0,1, an integer in 2,3 or 4.

The X in each polymer unit wherein ₃Can be arbitrarily-OH ,-Cl or

R wherein ₃, R ₄And R ₅Definition as above; R is the integer in 10 to 20000, and S is the integer in 1 to 4;

The X in each polymer unit wherein ₄Can be arbitrarily-OH, OCH ₃,-OCH ₂CH ₃Or

R wherein ₃, R ₄And R ₅Define as above, t is the integer in 10 to 20000; X is the integer in 1 to 4;

The X in each polymer unit wherein ₅At random be selected from-OH ,-Cl or substituting group:

R wherein ₃, R ₄And R ₅Definition as above; Y is the integer in 10 to 20000, and Z is the integer in 1 to 4;

The X in each polymer unit wherein ₆Be arbitrarily

-CH ₂CH(OH) CH ₂OH ,-CH ₂CH(OH) CH ₂Cl or

Wherein V is within 10 to 10000, and a is 6, and b is 1 to 4, and c is 1 to 4; R ₃, R ₄With

R ₅Definition as above;

The X in each polymer unit wherein ₇Can at random be-H ,-CH ₂CH(OH) CH ₂OH ,-CH ₂CH(OH) CH ₂Cl or

Wherein m is 1 to 4 integer, g within 10 to 10000, q, R ₃, R ₄And R ₅As defined above; Or

The X in each polymer unit wherein ₈, X ₉And X ₁₀Be arbitrarily-H ,-CH ₂CH(OH) CH ₂Cl or-CH ₂CH(OH) CH ₂OH or

Wherein q, R ₃, R ₄And R ₅Define as above, W is within 10 to 10000; Or

9. the mixture of polymeric chelates 1 to 8;

But each X in each aforementioned polymer inner complex (1 to 8) ₁, X ₂, X ₃, X ₄, X ₅, X ₆, X ₇, X ₈, X ₉And X ₁₀In-H ,-OCH ₃,-OCH ₂CH ₃,-Cl, or-OH and substituent total ratio must be between 10/90 to 90/10;

(2) oxidation polyvalent metal.

The present invention also relates to a kind of from containing H ₂Remove H in the fluid of S ₂The method of S, this method comprises:

(A) in contact area, make fluid under 10 ℃ to 90 ℃ temperature, contact for some time so that S with aqueous reaction solution ⁼Be oxidized to elementary sulfur effectively, reaction soln itself contains the above defined composition of significant quantity;

(B) make the aqueous phase separation that contains inner complex that produces in treated fluid and (A) step;

(C) from removing elementary sulfur through isolating aqueous phase the step (B);

(D) with the aqueous solution that contains the organic polymer inner complex of separation method treatment step (C) so that remove water and low molecular weight impurities effectively;

(E) process is concentrated with the inner complex aqueous solution of purifying and contact, make oxidizing polyvalent metal with the oxygenant of significant quantity;

(F) make the spissated inner complex aqueous solution of step (E) be circulated to the contact area of step (A).

In another embodiment, the organic polymer inner complex of going back the polyvalent metal of ortho states carried out oxidation before elementary sulfur is separated, and just in above-mentioned enforcement order, step (C) exchanges mutually with step (E).

In another embodiment, the present invention relates to a kind of from containing H ₂Remove H in the air-flow of S ₂The method of S, this method comprises:

(A) in contact area, make this air-flow under 10 ℃ to 90 ℃ temperature, contact for some time, so that effectively with S with a kind of aqueous solution ⁼Be oxidized to elementary sulfur, this solution contains the composition defined above and the oxygenant of significant quantity, so as effectively continuously again oxidation this go back the ortho states polyvalent metal;

(B) the gained solution that produces in separation bubble and the step (A);

(C) from the aqueous solution of step (B), remove elementary sulfur;

(D) with the aqueous solution that contains the organic polymer inner complex of separation method treatment step (C), remove water and low molecular weight substance effectively;

(E) will be recycled to the contact area of step (A) through the aqueous solution of the step (D) that concentrates and purify.

Fig. 1 illustrates the flow process of using (polyvalent metal) of the present invention organic polymer inner complex aqueous solution to come hydrogen sulfide contained in the oxidation fluid (as: fluid of geothermal well, the acid flow of " acid " property Sweet natural gas or refinery).Through oxidation H ₂S obtains elementary sulfur to be separated again.Again ionic organic polymer inner complex in the resulting as-reduced metal of oxidation returns to its original valence state with this metal, and uses dialysis or super-filtering method to concentrate and this aqueous solution of purifying.The organic polymer inner complex of the particularly ferric ion of continuous recycle metal, and reusable.This method is improved the known application of metallo-chelate, in order to eliminate the problem of environmental pollution that waste material that discharging contains poisonous and deleterious hydrogen sulfide causes.

Fig. 2 is similar to Fig. 1 in many aspects.The key distinction is when handling acid gas have the agent that reoxidizes of metallic polymeric chelates to exist at the beginning conversion zone.Therefore, reoxidize agent continuously with the Fe(II) inner complex is oxidized to the Fe(III) inner complex, and this mixture plays the effect of " on the spot " regenerated catalyst, thus left out the regeneration section of representing in Fig. 1 flow process.

Fig. 3 expresses and compares the degree of functioning that the iron polymeric chelates is oxidized to hydrogen sulfide sulphur with the monomer iron chelate.

Fig. 4 has compared a kind of monomer Fe(III) inner complex and two kinds of polymkeric substance Fe(III) inner complex is to the oxygenizement of sulfide ion.

About the application, use following definition:

Fluid stream

" fluid stream " among the present invention is meant any gas, liquid or gas-liquid mixed stream.These fluid streams comprise the acid gas stream that resembles geothermal heat flow, oil refinery, contain H ₂The Sweet natural gas of S and H ₂The S aqueous solution etc.

Water-soluble, polymeric chelate

Can chelating the oxidation polyvalent metal but be that any water-soluble, polymeric chelate of inert all can be used for present method in others.'inertia' is defined in the reaction and can arrive unallowed degree by damaging reaction in this article, and the weight-average molecular weight of polymeric chelates is better in 500 to 1000000 in the method for the invention.The weight-average molecular weight of polymeric chelates is better in 1000 to 500000.

A.L.Mc Crary etc. has summarized inner complex in " sequestrant " [Kirk-Othmer: " chemical industry technology complete works " (Encyclopedia of Chemical Technology), Volume 5, PP.339-368(1979)] literary composition.

Inner complex defined above with following array structure is good especially:

The X in each polymer unit wherein ₁Be arbitrarily-H or R-, R is-CH ₂COOH ,-CH ₂CH ₂COOH ,-CH ₂-P(=0) (

R wherein ₁And R ₂Can be arbitrarily-CH ₃,-SO ₃H ,-Cl ,-H or COOH, n is the integer in 5 to 20000; With

The X in each polymer unit wherein ₈, X ₉And X ₁₀Can be arbitrarily-H ,-CH ₂CH(OH) CH ₂Cl ,-CH ₂CH(OH) CH ₂OH or

Wherein q, R ₃, R ₄And R ₅Civilian as defined above described, W is within 10 to 10000.

R at the polymeric chelates (1 to 8) of preamble definition ₃, R ₄And R ₅In, better group is-CH ₂COOH and-CH ₂CH ₂COOH-CH ₂COOH is good especially.

The mixture expection of water-soluble organic polymer inner complex also can be used for the present invention.

The concentration of this polymkeric substance should reach every liter of solution can provide up to about 1 the gram chelation group level.Scope is 0.05 to 1 gram equivalent preferably.

Polymeric chelates described herein is by hereinafter described method preparation.In synthetic, be shown in table 1 with some polyamine and the polyethers that reach.

Table 1

Polyamine and polyethers as synthetic polymer sequestrant raw material

The amine polymerization degree (D.P) molecular weight ranges chain feature

E-100 ^a6 250-300 branching

PEI-6 ^b15 600 branching

Hydrolysis PEOx 50 ^c2000 linearities

Purifloc C-31 ^d500 ^e10000-30000 branching

Hydrolysis PEOx 500 ^f20000 linearities

PEI-600 1,500 60000 branching

Hydrolysis PEOx 5000 ^g500000 linearities

A.E-100-contains the lower molecular weight branched polymer of 6 the vinyl-amine groups of having an appointment for one kind, is the by product that quadrol is produced.

B.PEI is a polymine; PEOx, the Ju ethyl oxazoline.PEI is to be 60000 polymkeric substance (CORCAT600) by the molecular weight that Cordova Chemical Company obtains.By dry sample and solid element assay determination nitrogen content.

C.100% hydrolysis.

D.Purifloc C-31-is by Michigan State Midland (Michigan, Midland) polyvinylamine of Dow Chemical Company production.

E. also may be partial cross-linked.

F.85% hydrolysis.

G.97% hydrolysis.

In synthetic side group polymeric chelant (1 to 8), this technology often comprises side group is added on the adoptable main polymer chain.But not all sequestrant can both add on every kind of repeated polymerization unit of main polymer chain under reaction conditions.Therefore, the repeating unit in the inner complex 1 is:

Some X ₁Side group is-H, other then be-CH ₂COOH like:

In polymeric chelant (1 to 8), produce this class random addition of side group sequestrant group.If main polymer chain contain the side group epoxide group as:

, then after addition, if all epoxide groups further do not react chemical group-CH ₂CH(OH) CH ₂The OH(hydrolysis) or CH ₂CH(OH) CH ₂Cl is the side group on the main polymer chain.

The preparation label is 1 polymeric chelates

(X wherein ₁Be-H or-CH ₂COOH) example of (inner complex A) is that polymine (PEI150 or PEI600 have been bought by Dow Chemical Company) is soluble in water, then in the presence of highly basic with the excess chlorine acetic acid sodium reaction.

The preparation label is 1 polymeric chelates

[X wherein ₁Be-H or-CH ₂P(=0) (OH) ₂] another example of (inner complex B) be with polymine soluble in water and with phosphoric acid and formaldehyde reaction.The United States Patent (USP) 3974090 described monomer methods that are used for of R.S.Mitchell go for the polymkeric substance imines.

Produce by

(X wherein ₁Be-H or

, R ₁And R ₂Being respectively methyl) another example of polymeric chelates 1 of (inner complex C) definition is that polymine is soluble in water.Then with 2,4-xylenol and formaldehyde are handled.G.Grillot and W.Gomley.Jr. are being used for monomeric general technology applicable to the polymkeric substance imines described in " J.Amer, Chem, Soc " [Vol.67, PP, 1968ff(1945)].

Produce label and be 2 polymeric chelates [X wherein ₂Be-H or-CH ₂CH(OH) CH ₂N(CH ₂COOH) CH ₂CH ₂N(CH ₂COOH) ₂, P is 2000] and the example of (inner complex D) is at first to make Epicholorohydrin

(CH ₂Cl) produce with the ethylenediamine triacetic acid reaction

-N-(CH ₂COOH) CH ₂CH ₂N(CH ₂COOH) ₂, then react with polymine again.The above-mentioned technology that is used for inner complex A also can adopt.And, can replace quadrol with corresponding diethylenetriamine, triethylene tetramine and tetraethylene pentamine respectively to those polymkeric substance that q is 2,3 or 4.

Produce label and be 2 polymeric chelates [X wherein ₂Be-H or-CH ₂CH(OH) CH ₂[N(R ₃) CH ₂CH ₂] qN(R ₄) (R ₅), p is about 2000, q is 0, R ₄And R ₅Be respectively-CH ₂COOH] another example of (inner complex D-1) is that iminodiethanoic acid is soluble in water and add excessive about 20% Epicholorohydrin.With chlorinated hydrocarbons such as this product of dichloromethane extraction to remove unreacted Epicholorohydrin.Add 33% polyethyleneimine: amine aqueous solution such as CORCAT600 in this aqueous solution, heating and be to handle with sodium hydroxide under 9 to 10 the condition in the pH value need not be purified in addition and can be used this chelate solution.

The preparation label is 3 polymeric chelates [X wherein ₃Be-Cl ,-OH or-[N(R ₃) CH ₂CH ₂] sN(R ₄) (R ₅), S is 1, r is about 100, R ₃, R ₄And R ₅Be respectively-CH ₂COOH] example of (inner complex E) is to handle Polyglycol 166-450 with quadrol in the presence of alkali, handles with the excess chlorine sodium acetate again.

Produce label and be 4 inner complex (X wherein ₄Be-OH or-NH-[CH ₂CH ₂N(R ₃)] xCH ₂CH ₂N(R ₄)) (R ₅), t is 100, X is 1, R ₃, R ₄And R ₅Be-CH ₂COOH) example of (inner complex F) is to handle polyethyl acrylate with diethylenetriamine, handles in the presence of highly basic with sodium chloroacetate again.

Produce label and be 5 inner complex (X wherein ₅Be-Cl ,-OH or-[N(R ₃) CH ₂CH ₂] zN(R ₄) (R ₅), R ₃, R ₄And R ₅Be-CH ₂COOH, Y are 100, and Z is 1) example of (inner complex G) is to handle in the presence of highly basic with quadrol to gather (vinyl chloride).In the presence of alkali, handle this product with the excess chlorine sodium acetate again.Replace quadrol with diethylenetriamine, triethylene tetramine etc., can make more high-grade homologue.

Produce label and be 6 inner complex (wherein-X ₆Be-CH ₂CH(OH) CH ₂OH or-CH ₂CH(OH) CH ₂[N(R ₃) CH ₂CH ₂] cN(R ₄) (R ₅), R ₃, R ₄And R ₅Be-CH ₂COOH, C are 1) example of (inner complex H) is to use ethylenediamine triacetic acid, handles industrial copolymer KYMENE557 H(by Delaware State Wei Mingdun (Delaware, Hercules Corporation Wilmingtan) makes)

Produce label and be 7 inner complex (X wherein ₇Be-H or-CH ₂CH(OH) CH ₂[N(R ₃)-CH ₂CH ₂] cN(R ₄) (R ₅), m is 1, and g is 1000 approximately, and q is 1, R ₃, R ₄And R ₅All be-CH ₂COOH, m are 1) example of (inner complex J) is that the polymkeric substance of methacrylic acid and quadrol and ethylenediamine triacetic acid are reacted.

A kind of label is that 8 inner complex is X wherein ₈, X ₉And X ₁₀Be respectively-H ,-CH ₂CH(OH) CH ₂OH or-CH ₂CH(OH) CH ₂-N(R ₃) CH ₂CH ₂N(R ₄) (R ₅), R ₃, R ₄And R ₅Be-CH ₂COOH.By commodity FIBRABON35(Diamend Shamrock Co. is sold) in the presence of alkali, react and make this side group affixture (inner complex K) with ethylenediamine triacetic acid

General every in polymeric chelates 1 to 8-X ₁To X ₁₀In-H(or OCH ₃, OCH ₂CH ₃, OH or Cl) with the ratio of substituting group in about scope of 10/90 to 90/10, better within 10/90 to 40/60.

The preparation method who narrates these organic polymer inner complexs in more detail below is as the embodiment part.

Polyvalent metal

Generally, but oxidation state and go back ortho states all any polyvalent metal of chelating all can be used for the metal ingredient of the present invention as polymeric chelates, but with iron, copper and manganese for well.And be best with iron.This polyvalent metal chelates should be able to be reduced to himself the hydrogen sulfide oxidation accordingly the metallo-chelate than lower valency, then in typical redox reaction can by oxygen or similarly oxidation reaction method be oxidized to the metallo-chelate of higher valence state.Operable other polyvalent metal comprises tin, lead, platinum, tungsten, nickel, palladium, chromium, cobalt, vanadium, titanium, tantalum, zirconium and molybdenum.

The separation method of water and low molecular weight substance:

The separation method that organic polymer inner complex and water and water miscible low molecular weight product and material are separated can adopt any single or hybrid technique applicable to this purpose.Use film separation methods such as ultra-filtration and/or dialysis better.It is better that the film that employing has various synthetic polymers of shapes such as film, tubular fibre carries out ultra-filtration.Be particularly useful as to removing the film class that water and low molecular weight substance keep water-soluble, polymeric chelate simultaneously (can have been bought by Massachusetts Danville's Amicon Company) such as UM05, UM2, PM10 arranged.

R.R.Klinknowski is at " Kirk Othmer: chemical industry technology complete works " (Vol.23, PP.439-461) narrated super-filtering method in (1983), (Vol.7, PP.564-579) (1979) have narrated dialysis technology and technology to E.F.Leonard in this book.

In Fig. 1, the acid gas stream in the pipeline 1, as useless geothermal heat flow or useless natural gas flow [contain the 1.0%(volume of having an appointment) H ₂S] or the exhaust flow of refinery [the highest 1.0%(volume of having an appointment that contains) H S] enter column 2, wherein contain the mixture of the aqueous solution (about 1 mole of concentration) of water-soluble, polymeric chelate, this inner complex as described herein contains the oxidation state polyvalent metal.With Fe ^{+ 3}For good, the back will with and Fe ^{+ 3}Be appreciated that at this used Fe ^{+ 3}(oxidation state) and Fe ^{+ 2}(going back ortho states) can represent any similar polyvalent metal.The intake pressure general requirement is not strict, can be per square inch between 10 to 1000 pounds (Psig), and pascal unit is that 169 kPas (KPa) are between the 6858KPa.And with 15 to 100psig pressure range (203KPa to 777KPa) for well.The temperature of aqueous mixture is between 10 ℃ to 90 ℃, and with 20 ℃ to 80 ℃ for well.Better at 20 ℃ to 50 ℃.Suitable duration of contact between aqueous mixture and the sour gas usually between 1 second to 5 minutes, and with between 2 seconds to 1 minute for well.Generally be enough to whole sulfide ions during this period of time and be oxidized to elementary sulfur (S °) substantially.Then, the air-flow through purification or desulfurization leaves zone 2 by pipeline 3.In general, the Purge gas of the discharging in the pipe 3 can satisfy the H of U.S. environment emission standard ₂The S standard.

In aqueous mixture, hydrogen sulfide is contained the Fe(III) polymeric chelates be converted into element sulfur particle.Fe(III in the while polymeric chelates) is reduced to the Fe(II).Discharge continuously through pipeline 4 and to contain sulphur solid particulate and water-soluble Fe(II) aqueous mixture of polymeric chelates, also can add the degassing and pressure regulating equipment 5.Remaining gas is emitted by pipeline 6.

The separation of sulphur and remove can be according to a conventional method as precipitation, centrifugal separation method is realized.Not processed aqueous mixture is delivered to tripping device 8 through pipeline 7.Device 8 is a sets filtering device preferably.Through pipeline 9 these steps the time, needn't remove whole sulphur.The personnel that are familiar with this technology can adjust some conditions to reach suitable liquid stream and air-flow drainage rate.

The aqueous solution that contains polymeric chelates that has removed elementary sulfur is delivered to second tripping device 11 through pipeline 10.This separator uses certain methods excessive separation water and low molecular weight product and by product.General employed method is super-filtering method or dialysis method, and with super-filtering method for well.Water and molecular weight are lower than 1000, preferably are lower than 500 low molecular weight substance such as EDTA and separate and transfer out, dispose with environment acceptable form again through pipeline 12.Through pipeline 13 spissated waterborne polymeric inner complex is delivered to regeneration zone 14 then.

At regeneration zone is in the column 14, and this mixture and the oxygenant that enters through pipeline 15 such as excess air or oxygen contact, and make the Fe(II) polymeric chelates is converted into the Fe(III) polymeric chelates.The temperature of this column can change between 0 to 50 ℃, with between 20 ℃ to 40 ℃ for well, pressure is at 10 to 100 pounds/square inch (169 handkerchiefs and 777 handkerchiefs), with better at 20 to 50 pounds/square inch (236 handkerchief to 439 handkerchiefs).

To contain then oxidized metal [the Fe(III) polymeric chelates be delivered to contact area 2 through pipeline 16, restart this circulating reaction process.If desired, can in process, add make up water, polymeric chelates and polyvalent metal through pipeline 17.

In the present invention, the order that is shown in the technological process among Fig. 1 also can have some changes.These changes comprise the separator 8 of commutative element sulphur and remove the position of the separator 11 of water and low molecular weight substance.Separable a part of water and low molecular weight substance in the presence of the element sulfur particle that still produces to some extent like this, but elementary sulfur may be easy to stop up the hole of amicon or permeable membrane.

Another change that is shown in the method for the present invention of Fig. 1 is to remove tripping device 11, pipeline 10 and 13 is connected, and will installs 11 and be connected on the circulation line 16, makes it be in regenerating unit 14 and makes up line 17 between the point of connection on the pipeline 16.A difficulty that is run in this configuration is that device 14 will be handled a large amount of water fluids.

In Fig. 2, some units are as 1 to 12 corresponding to the similar unit of numbering among Fig. 1, and have same effect basically.In this flow process, add oxygenant such as oxygen to contact device 2 through pipeline 1A, simultaneously through pipeline 1 with the Fe(III) water-based organic polymer inner complex add.In this flow process, along with the H that exists ₂When S is oxidized to elementary sulfur, Fe(III), be reduced to the Fe(II), the Fe(II of Sheng Chenging simultaneously) dioxygen oxidation that existed is the Fe(III).Following reaction formula can be illustrated:

H ₂The S+2[Fe(III). polymeric chelates] →

+ 2H ⁺+ 2[Fe(III). polymeric chelates]+S °

1/2O ₂(gas)+H ₂The O+2[Fe(II). polymeric chelates] →

20H ^-+ 2[Fe(III). polymeric chelates]

Comprehensive these reaction formula, entire reaction can be represented by following reaction formula:

As shown in table 2, the content of iron is in the scope of 0.03M in many polymeric chelatess.Because the stability of inner complex, inner complex concerns little with the ratio of iron and total iron level.As shown in table 2, because the W value is the mol ratio of nitrogen and iron in when beginning precipitation sequestrant (polymeric chelant) under the room temperature, so this value is very important.This value representation the maximum level of iron in the inner complex.

Table 2

Polymeric chelant is to the sequestering action of iron (III)

Ratio W is the mol ratio of nitrogen and iron in chelating monomer or the polymkeric substance when beginning to precipitate under the room temperature.The pH value of all tests is 7 ± 0.5

Inner complex (Fe), M W

-????-????-

EDTA????0.03????2.0

MBEDTA????0.03????2.2

Sym，EDDT????0.03????＞10

DTDA????0.015????＞9

DTPA????0.03????2.5

TTHA????0.05????2.3

CM????E-100????0.04????3.4

CM????PEI6????0.045????3.2

CM????PEOx，DP-50????0.025????5

CM????PEOx，DP-100????0.025????4

CM????PEOx，DP-1000????0.015????4.2

CM????C-31（Puriflocc（-31）????0.04????5

（DOW）

The EDTA-ethylenediamine tetraacetic acid (EDTA)

MBEDTA-methyl-right-benzyl ethylenediamine triacetic acid

Sym.EDDA-symmetry ethylenediamine-N,N'-diacetic acid(EDDA)

DTDA-diethylenetriamine oxalic acid

DTPA-divinyl tetramine pentaacetic acid

The TTHA-triethylenetetramine hexaacetic acid

The CM-carboxymethyl

The PEI-polymine

PEOx-Ju Yi Xi oxazoline

Fig. 3 relates in air Fe(III when sulfide oxidation is elementary sulfur) influence of the catalytic amount of polymeric chelates.Its condition is [S ⁼].=30ppm=0.00188N; Sequestrant=CM PEI150=carboxymethyl polymine, MW=15000; PH=7.8 ± 0.2, [N(CH ₂CH ₂OH) ₃]=0.01N; Air velocity=200 ml/min.Used symbol is: O refers to the Fe(III) inner complex, the Fe(III): [S ⁼]=1: 10; △ refers to not have the Fe(III) inner complex.

Fig. 4 relates to Fe(III in air) polymeric chelates is to the oxygenizement of sulfide.Its condition is: [the Fe(III)].＝[S ^＝]。=0.00188N; PH=7.8 ± 0.2, [N(CH ₂CH ₂OH) ₃]=0.01N; Air velocity=200 ml/min.Used symbol is: △=HEDTA=ethylenediamine triacetic acid, Fe/N=1: 2; O=CMPEI6,=CM PEI150; Fe/N=1: 4; CM PEI is the carboxymethylation polymine.

The following example does not mean that any restriction only as an illustration.Side group X among the embodiment in the polymerized unit of each polymkeric substance ₁To X ₁₀Be selected from those side groups of the label of indicating.Can know by described herein,, just can as requested all or part of chelating side group be added on the main polymer chain as long as adjust the synthesis condition of experiment.That is to say,, can adopt the short reaction times if only need part replace, lower reactant concn, lower temperature of reaction reaches those methods known to the personnel that are familiar with this art.If need be in addition on the main polymer chain more or whole chelating side groups, then adopt long reaction times, higher reactant concn and higher temperature of reaction.

Polymericular weight as herein described is generally represented by weight-average molecular weight.

Embodiment 1[is based on the organic polymer inner complex 1 of polymine (PEI)] (inner complex A:X ₁Be-H or-CH ₂COOH)

The solution (being as the criterion with the nitrogen in the amine) of 1.25 volumetric molar concentrations will be made in polymine 11 gram (polymerization degree DP1500) water-soluble (200 milliliters).Interpolation sodium chloroacetate (31 grams, excessive 5%) is maintained at about 60 ℃ with this reaction mixture simultaneously in stirring down in this aqueous solution.Using pH electrode to monitor this reaction and adding 50% sodium hydroxide keeps its pH value more than 10.Reaction is carried out stopping this reaction after 40 minutes, and makes the reaction mixture cooling.This aqueous solution is diluted to 1.0 volumetric molar concentrations (in the nitrogen in the amine), no longer purifies and to use.

Embodiment 1 A(prepares polymeric chelates 1) (inner complex B:X ₁Be-H or-CH ₂P(=0) (OH))

In 500 ml flasks that water condenser and dropping funnel are housed, add the phosphorous acid (also containing 9.4 gram hydrogenchloride) of 99 gram (0.6 moles) 49.9% and the hydrochloric acid of 5.2 grams 37%.The mole total amount of used hydrogenchloride is 0.4.Add 14 gram CORCAT150(Cordova Chemical Co. then) (for 33% the aqueous solution of the polymine that contains 0.1 mole of amine nitrogen), make the heating of gained mixture.Added in 8-10 minute and reunite amine, reaction mixture temperature reaches about 70-75 ℃ simultaneously.Then reaction mixture was heated to boiling point about 20 minutes, and made boiling point thus at 110-115 ℃ homogeneous transparent solution.The gained transparent aqueous solution is kept about 2 hours at boiling point, and add the Paraformaldehyde 96 of 22 grams (0.66 mole).After two hours, make this transparent reaction mixture keep seething with excitement 30 minutes and making it be cooled to about 25-30 ℃ again.Clear solution is amber, contains the 50%(weight of having an appointment) the polymine phosphoric acid ester, no longer purify and can use.

Embodiment 1 B(prepares polymeric chelates 1) (inner complex C:X ₁Be-H or 6-methylene radical-2 the 4-xylenol):

To 13 gram polymine CORCAT150(Cordova Chemical Company) add 10.8 in the aqueous solution (33%) of (containing 0.1 mole in effective amine nitrogen) and restrain 2,4-xylenol (0.1 mole).This solution is being remained on below 20 ℃, and slowly adding 37% formalin (0.11 mole), stirring simultaneously.At room temperature solution was placed 1 hour, be warmed to then 80 ℃ 2 hours.This solution can use without purifying in the test of back

Embodiment 2(prepares polymeric chelates 2) (inner complex D:X ₂=-H or-CH ₂C H(OH) CH ₂N(CH ₂COOH) CH ₂CH ₂N(CH ₂COOH) ₂)

Carry out this preparation feedback in two steps: (1) is connected quadrol on the polymer chain; (2) amine is converted into ethylenediamine triacetic acid (ED3A).

Step (1) is dissolved in 23.5 gram Polyglycol 166-450 (0.25 mole of monomer unit) and 94 grams, 85% quadrols (1.3 moles) in 50 milliliters of Virahols and the 25 milliliters of toluene and backflow (about 100 ℃ 6 hours.Along with reaction is carried out, add Virahol to keep its homogeneity, the iso-propanol/toluene of final system is about 75/25.Follow the tracks of reaction with the chlorion in the silver nitrate titration aliquot solution.Then add the NaOH(0.25 mole of 20 grams 50%), filter resulting solid NaCl, use washing with alcohol again, and remove liquid with vacuum-evaporator at 55 ℃.Although still have NaCl residual in the product, the gained ultimate analysis is C: H: the N mol ratio is 4.6: 12.1: 2.00(expection mol ratio is 5: 12: 2)

Step 2: this intermediate product is dissolved in about 200 ml waters, adds 3.3 moles of sodium chloroacetates to every mole of nitrogen wherein.Be about at about 60 ℃ at 10 o'clock with the pH value and kept this system about 1 hour.This moment, filtering white depositions (estimation is NaCl) was adjusted to the iso-electric point that 2(expects with the pH value), there are a large amount of white solids to form at this point.Leach this solid and find that this solid is EDTA, estimation is because unreacted quadrol does not remove fully and forms when vacuum-evaporation.This filtrate is carried out dialysis with respect to 4 premium on currency.

Use the Fe(III) a aliquots containig of titration, estimate the EDTA content in (polymkeric substance) material of dialysis.Find that about 1/3 predetermined sequestrant group is present in the polymkeric substance.

Embodiment 2 A(prepare polymeric chelates 2) (inner complex D-1:P=2000, X ₂Be-H or-CH ₂CH(OH) CH ₂N(CH ₂COOH) ₂)

The imino-acetic acid of 14.3 grams (0.1 mole) is dissolved in 100 ml waters, in this solution, adds the Epicholorohydrin of 0.12 mole (excessive approximately 20%).This solution is at room temperature placed after 1 hour with 50 milliliters of dichloromethane extractions, to remove unreacted Epicholorohydrin.Add 14.7 to stripped aqueous phase and restrain 33% polymine CORCAT600(Cordova Chem.Co.Muskegon, Michigan) solution wherein contains 0.1 mole nitrogen after measured.This solution is heated to 60 ℃, is the speed interpolation sodium hydroxide solution (10N) of 9 to 10 scope to be enough to keep pH value simultaneously.Afterreaction was finished in 30 minutes, contained the polymine that has the imino-acetic acid group in the gained solution now, promptly can be used for later test without purifying.

Embodiment 3(prepares polymeric chelates 3) (inner complex E:X ₃Be-OH ,-Cl or-[N(CH ₂COOH) CH ₂CH ₂] N(CH ₂COOH) ₂)

The ethylenediamine triacetic acid of 224 grams (0.1 mole) is dissolved in 100 ml waters.0.12 mole about 20% excessive Polyglycol 166-450 of interpolation in this solution [HYDRIN10 * 1(DP-40)], for the B.F.Goodrich Co. of joslyn hi-voltage produces, be dissolved in toluene/methylene dichloride (50/50; V/V) in.Add tetrabutylammonium chlorine (0.01 mole) as phase-transfer catalyst.Stirred this solution one hour under the room temperature.By adding the HCl neutralization that sodium hydroxide makes generation.Without purify can use this waterborne polymeric inner complex thereafter.

Embodiment 4(prepares polymeric chelates 4) (inner complex F:X ₄Be-OH or-NHCH ₂CH ₂N(CH ₂COOH) CH ₂CH ₂N(CH ₂COOH) ₂)

To gather (methyl acrylate) (86 restrain, and are equivalent to the formula weight of a mole of monomer methyl acrylate) and be dissolved in about 300 milliliters of toluene, and add 520 gram diethylenetriamines (5 moles).With this solution be heated to 40-50 ℃ one hour and steam to remove excess amine and toluene in a vacuum.Residuum is dissolved in 500 ml waters and to this solution add 348 gram sodium chloroacetates (3.0 moles) and be heated to about 60 ℃ 30 minutes, be that the speed of 9-10 is added sodium hydroxide to be enough to keep pH simultaneously.This solution has desired structure, is available test thereafter without purifying in addition.

Embodiment 5(prepares polymeric chelates 5) (inner complex G:X ₅Be-OH or-N(CH ₂COOH) CH ₂CH ₂N(CH ₂COOH) ₂, Y is 100)

Polyvinyl benzyl chloride (15 grams are equivalent to 0.1 mole monomeric unit) is dissolved in 100 milliliters of methylene dichloride, and adds 30 gram quadrols (0.5 mole).This solution is warmed to 40 ℃, stirred 2 hours.Under vacuum, remove excess amine and methylene dichloride.Resulting polymers is dissolved in 200 ml waters and as in the past the used method of embodiment carry out carboxymethylation reaction.Resulting polymers has required structure and can use without purifying.

Embodiment 6(prepares polymeric chelates 6) (inner complex H:X ₆Be-H or-(CH ₂CH(OH) CH ₂N(CH ₂COOH) CH ₂CH ₂N(CH ₂COOH) ₂):

In the solution (excessive two times) of 46 gram ethylenediamine triacetic acids, add 80 gram polymkeric substance KYMENE557 H(0.1 mole of monomer equivalents at about 200 ml waters) (Hercules Corporation, Delaware State Wei Mingdun) (polymkeric substance of oxalic acid, diethylenetriamine and Epicholorohydrin).With this solution be heated to 80 ℃ two hours.Without purify can with containing of gained required polymkeric substance 6 solution be used for thereafter test.

Embodiment 7(prepares polymeric chelates 7) (inner complex J:X ₇Be-H or-CH ₂CH(OH) CH ₂N(CH ₂COOH)-CH ₂CH ₂N(CH ₂COOH) ₂, m is 1, g is about 100):

In the polymers soln that the reaction of methyl acrylate and quadrol equimolar amount is made, add the Epicholorohydrin for preparing among embodiment 2 A and the solution of iminodiethanoic acid affixture by equimolar amount.This solution is heated to 80 ℃, and (2 hours, resulting polymers promptly can be used for test thereafter.

Embodiment 8(prepares polymeric chelates 8) (inner complex K:X ₈, X ₉And X ₁₀Be-H ,-CH ₂CH(OH) CH ₂OH or-CH ₂CH(OH) CH ₂N(CH ₂COOH) CH ₂CH ₂N(CH ₂COOH) ₂): the industrial copolymer Fibrabon35 (Diamand Shamrock Corporation joslyn hi-voltage) that 54 grams is contained the active Epicholorohydrin group of 100 mmoles mixes mutually with 46 gram ethylenediamine triacetic acid (0.2 mole) solution, this solution is heated to 60 ℃, and to be enough to the keeping speed of the about 9-10 of pH value to add sodium hydroxide.After two hours, reaction is finished, and this solution can be used in thereafter the test.An X is arranged in each polymer unit approximately ₈, X ₉And X ₁₀It is the inner complex side group.

The dialysis of embodiment 9(iron polymeric chelates)

In the dialysis process, 100 milliliters of iron organic chelates (be made into iron content and be about 0.1 volumetric molar concentration) dialysis in 2 liters of deionized waters is spent the night.The poly-sequestrant of CM PEI150 and CM PEI600 is the SPECTROPOR1(Van Waters ε Rogers of about 6000-8000 by nominal by molecular weight, San Francisco) carry out dialysis.In both cases, lose the iron of 3%-5% approximately.By SPECTROPOR6(Van Water ε Rogers, be 2000 by molecular weight) CM PEI6 solution is carried out dialysis.In this case, lose 10% iron approximately.

The ultra-filtration of the poly-inner complex of embodiment 10(iron):

Carry out ultra-filtration test in Amicon Model52 pond, this pond is a cylindrical vessel, is that the film of 43 millimeters (or 12.5 centimetres) is as the bottom surface with a diameter.This pond volume is about 60 milliliters and the outstanding influence of stirring rod with the minimizing polarized action that be magnetic.In test, 25 ml solns are placed this pond and the air line that this gas space and pressure remain on 15 pounds/square inch (203 kPas) joined.

Using three kinds of films in this research, is the product of Massachusetts Danville's Amicon Corpara-tion approximately.These films are called UM05, UM2 and PM10, and the molecular weight that ends of its nominal is respectively 500,1000 and 10000.Thiocyanate-method with standard is measured iron level.

The results are shown in down tabulation 3.

Table 3

The ultra-filtration of iron polymeric chelates and dialysis

Poly-sequestrant film

UM05????UM2????PM10

Detention detention flow detention flow

% % gsfd ^＊% gsfd ^＊

CM????PEI600????89????98????1.3????91????6

CM????PEI600????99????2.8????95????16

Dialysis

CM????PEI150

Dialysis 95 1.4 97 9

CM????PEI6????80-90????0.8????25????28

CM????PEI6

Dialysis 61 90＜0.3

CME-100????84????92????0.6????27????40

EDTA????23????10????1

Deionized water 5 100

[CM PEI-carboxymethyl polymine etc.]

Detention % value is the mean value of stable state part in the experiment.

Flux values is interpolation or the value that is extrapolated to 0.10M Fe place.

Detention %-can not be by film the amount of inner complex (or other material).

^*Gsfd=gallon/square feet * fate

As seen from Table 3, by molecular weight ranges be the ultra-filtration thickness detention reasonably well of 1000-10000 with carboxymethylation polymine 6(CM PEI6, about 15 monomeric units) be the poly-inner complex of main body or bigger polymkeric substance.With Amicon UM2 film (being about 1000) detention in a large number (80-90%) CM PEI6, but be about 10000 by molecular weight with PM10(by molecular weight) detention very poor (20-30%).With equal higher polymkeric substance CM PEI150 and the CM PEI600(95-99% of detention molecular weight effectively of these two kinds of films).

For the poly-sequestrant of table in the III, be 15 pounds of/square inch (203KPa) chelated irons (III) concentration when being 0.1M at pressure, the dialysis amount of Amicon UM2 film is about 1 gallon every square feet of every day.For the PM10 film, dialysis is to be every square feet of 6-30 gallon every day.Dialysis amount and concentration of iron are relative.

Embodiment 11(removes sulfide ion)

The trolamine that uses 0.01M is with 100 milliliters of sodium sulfide solution (S of 30ppm ⁼, 0.00094 volumetric molar concentration) and to be buffered in pH be 7.8.Flow with 200 ml/min blasts air and timing sampling mensuration sulfide ion concentration by solution.S ⁼Minimizing be shown in Fig. 3.With iron content (III) inner complex concentration is that the solution of 0.000188 volumetric molar concentration carries out identical test, this concentration for iron be with the sulfide direct oxidation sulphur metering concentration 1/10th.The minimizing of sulfide also is shown in Fig. 3, and significantly quickens when inner complex is arranged.Polymeric chelates is carboxymethyl polymine PEI150-[CH ₂CH ₂-N(CH ₂COOH)] dp, its polymerization degree (dp) is about 300.

From Fig. 4 as seen, when using tfe polymer (III) inner complex, S ⁼The decline of concentration is only slightly slow when using monomer iron (III) inner complex.

Fig. 4 has compared Fe(III when using above-mentioned condition) inner complex is to the oxygenizement of sulfide.From Fig. 4 as seen, in 2 to 3 minutes, two kinds of polymeric chelates CM PEI6 are the same with the monomer inner complex with CM PEI150 effective.

Embodiment 12(is through circularly removing H ₂S)

The H that will discharge by geothermal well ₂S concentration is 0.99%(weight) air-flow introduce contact jar, also introducing in jar and contain 1.0%(weight, is benchmark with the amount of the mixture) as the Fe(III) carboxymethyl polymine (CM PEI6) aqueous mixture of polymeric chelates.The excessive 10%(mole of inner complex that adds is a benchmark with iron), the pH value of system is 6.The pressure of feed gas is about 15 pounds/square inch (203 kPas), and the temperature of mixture is about 35 ℃.Be about 60 seconds duration of contact.The Fe(III) polymeric chelates is with H ₂S is converted into elementary sulfur, simultaneously the Fe(III) polymeric chelates is reduced to the Fe(II) polymeric chelates.The sulphur that is generated is fine particulate and with its filtering separation.Use Amicon UM2 film and equipment this aqueous solution to be handled with the ultra-filtration method.CM PEI6 retains in the water solution system, and low molecular weight material (being lower than 1000) is removed.Contain CM PEI6 Fe(II with oxygen treatments applied) the aqueous solution make iron (II) be oxidized to iron (III) again and be circulated to the contact jar.

Embodiment 13(removes H ₂S makes the oxidation of iron (II) inner complex simultaneously)

In the exposure chamber, introduce the Oxygen Flow of 2 ml/min as shown in Figure 2 simultaneously, to the H of embodiment 12 ₂The S air-flow is handled.H ₂S is oxidized and remove with the form of elementary sulfur, contains CM PE I6 Fe(III) the aqueous solution recycle.

Though this paper enumerates and narrated a small amount of embodiments of the invention, concerning the personnel that are familiar with this technology, can under the situation that does not break away from main idea of the present invention and scope, from fluid, remove H obviously to using the polymer metal inner complex ₂S and S ⁼Method do a little improvement and change.All these improvement carried out within the scope of the appended claims and change all are included within the present invention.

Claims (8)

1, a kind of from containing H ₂Remove H in the fluid of S ₂The method of S, this method comprises:

(A) this fluid is contacted 10 ℃ to 90 ℃ temperature with aqueous reaction solution at contact area and be enough to make S ⁼Be oxidized to the time of elementary sulfur, this reaction soln itself contains the composition of significant quantity, and said composition contains

1) water-soluble organic polymer inner complex, wherein, the weight-average molecular weight of inner complex is between 1000 to 500000, and the component of polymer of inner complex is:

The X in each polymer unit wherein ₁Can be arbitrarily-H or R-, R be-CH ₂COOH ,-CH ₂CH ₂COOH ,-CH ₂-P (=O) (OH) or

R wherein ₁And R ₂Can be arbitrarily-CH ₃,-SO ₃H ,-Cl ,-H or-COOH, n is the integer between 5 to 20000;

The X in each polymer unit wherein ₂Be-H ,-CH ₂CH (OH) CH ₂OH ,-CH ₂CH (OH) CH ₂Cl or

R wherein ₃, R ₄And R ₅Be integer between 5 to 20000 for P arbitrarily separately; Q is an integer 0,1,2,3 or 4;

The X in each polymer unit wherein ₃Can be arbitrarily-OH, Cl or

R wherein ₃, R ₄And R ₅Definition as above; R is the integer between 10 to 20000, and S is the integer between 1 to 4;

The X in each polymer unit wherein ₄Can be arbitrarily-OH ,-OCH ₃,-OCH ₂CH ₃Or

R wherein ₃, R ₄And R ₅Define as above, t is the integer between 10 to 20000; X is the integer between 1 to 4;

The X in each polymerized unit wherein ₅Can be arbitrarily-OH ,-Cl or

R wherein ₃, R ₄And R ₅Definition as above; Y is the integer between 10 to 20000, and Z is the integer between 1 to 4;

The X in each polymerized unit wherein ₆Can be arbitrarily-CH ₂CH (OH) CH ₂OH ,-CH ₂CH (OH) CH ₂Cl or

Wherein V is the integer between 10 to 10000, and a is 6, and b is 1 to 4, and C is 1 to 4; R ₃, R ₄And R ₅Definition as above;

The X in each polymer unit wherein ₇Can be arbitrarily-H ,-CH ₂CH (OH) CH ₂OH ,-CH ₂CH (OH) CH ₂Cl

Wherein m is 1 to 4 integer, and g is between 10 to 10000, q and R ₃, R ₄And R ₅Definition as mentioned;

The X in each polymerized unit wherein ₈, X ₉And X ₁₀Can be arbitrarily-H ,-CH ₂CH (OH) CH ₂Cl, CH ₂CH (OH) CH ₂OH or

Wherein q, R ₃, R ₄And R ₅Define as above, W is between 10 to 10000; Or

(9). the mixture of polymeric chelates 1 to 8; Its restricted condition is each X in above-mentioned each polymeric chelates (1 to 8) ₁, X ₂, X ₃, X ₄, X ₅, X ₆, X ₇, X ₈, X ₉Or X ₁₀In-H ,-OCH ₃,-OCH ₂CH ₃,-Cl or-OH and substituent total ratio is about between 10/90 to 90/10;

2) a kind of oxidation state polyvalent metal;

(B) with the water and the pneumatic separation that obtain in the step (A);

(C) remove elementary sulfur from the isolated aqueous phase of step (B);

(D) with the aqueous solution that contains polymeric chelates that generates in separation method separation and the purifying step (C), remove effectively and anhydrate and low molecular weight substance;

(E) concentrated aqueous solution with the metal-containing polymer inner complex of generation in the step (D) contacts with the oxygenant of significant quantity, makes oxidizing polyvalent metal;

(F) concentrated aqueous solution of step (E) is recycled to the contact area of step (A).

2, a kind of from containing H ₂Remove H in the air-flow of S ₂The method of S, this method comprises:

(A) 10 ℃ to the temperature of 90 ℃ of scopes, make air-flow in contact area, contact certain hour with the aqueous solution, make H effectively ₂Sulphur among the S is oxidized to elementary sulfur, and this reaction soln itself contains composition and a kind of oxygenant of the claim 1 of significant quantity, and this oxygenant can make the polyvalent metal oxidation again of going back ortho states effectively continuously.

(B) water-phase product that generates in air-flow and the step (A) is separated;

(C) from removing elementary sulfur by isolating aqueous phase the step (B);

(D) with the aqueous solution that contains the organic polymer inner complex that generates in separation method separation and the purifying step (C), remove effectively and anhydrate and low molecular weight substance;

(E) concentrated aqueous solution that generates in the step (D) is recycled to the contact area of step (A).

3, according to the method for claim 1 or 2, wherein the oxidation state polyvalent metal in the step (A) is a copper.

4, according to the method for claim 1 or 2, wherein the oxidation state polyvalent metal in the step (A) is an iron.

5, according to the method for claim 1 or 2, wherein the aqueous solution in the step (D) selects for use the film separation method of ultra-filtration or dialysis to concentrate.

6, according to the method for claim 5, film separation method wherein is a super-filtering method.

7, according to the method for claim 1 or 2, inner complex wherein is a composition 1 as defined in claim 1.

8, according to the method for claim 1 or 2, inner complex wherein is a composition 8 as defined in claim 1.

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