CN113245067B - Guar gum base compound and preparation method thereof, zinc-sulfur separation inhibitor and zinc-sulfur flotation separation method, flocculant and application thereof - Google Patents

Guar gum base compound and preparation method thereof, zinc-sulfur separation inhibitor and zinc-sulfur flotation separation method, flocculant and application thereof Download PDF

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CN113245067B
CN113245067B CN202110696528.7A CN202110696528A CN113245067B CN 113245067 B CN113245067 B CN 113245067B CN 202110696528 A CN202110696528 A CN 202110696528A CN 113245067 B CN113245067 B CN 113245067B
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zinc
guar
sulfur
guar gum
based compound
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CN113245067A (en
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熊伟
路亮
张行荣
朱阳戈
吴萌
陈雁南
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Beijing General Research Institute of Mining and Metallurgy
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00Flotation
    • B03D1/001Flotation agents
    • B03D1/004Organic compounds
    • B03D1/012Organic compounds containing sulfur
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00Specified effects produced by the flotation agents
    • B03D2201/002Coagulants and Flocculants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00Specified effects produced by the flotation agents
    • B03D2201/06Depressants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03DFLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00Specified materials treated by the flotation agents; specified applications
    • B03D2203/02Ores

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Abstract

The application provides a guar gum base compound and a preparation method thereof, a zinc-sulfur separation inhibitor and a zinc-sulfur flotation separation method, a flocculating agent and application thereof. Guar-based compounds having the general structural formula:
Figure F_210603141608695_695617001
wherein R is1‑R9Each independently is a hydrogen atom or a functional group capable of interacting with a metal ion and R1‑R9At least one of which is not H. A method of preparing a guar-based compound comprising: the guar gum-based compound is obtained by reacting a compound comprising guar gum and a functional group capable of interacting with a metal ion. The zinc-sulfur separation inhibitor includes a guar-based compound. A zinc-sulfur flotation separation method comprising: adding the zinc-sulfur separation inhibitor into the ore pulp for flotation. The flocculant comprises a guar-based compound. The application of the flocculant is used for mineral separation or wastewater treatment. The guar gum base compound provided by the application has excellent flocculation effect and biocompatibility, and is simple and convenient to synthesize.

Description

Guar gum base compound and preparation method thereof, zinc-sulfur separation inhibitor and zinc-sulfur flotation separation method, flocculant and application thereof
Technical Field
The application relates to the field of natural macromolecular compounds, in particular to a guar gum base compound and a preparation method thereof, a zinc-sulfur separation inhibitor and a zinc-sulfur flotation separation method, a flocculating agent and application thereof.
Background
Guar gum is a natural polyhydroxy polysaccharide macromolecular compound, and the polyhydroxy structure in the molecular structure of the guar gum enables the guar gum to easily form hydrogen bonds in water, so that the guar gum has the incomparable advantages of other natural biological macromolecules in application. The hydroxyl group in the guar molecule is also a good molecular modification site, so that the guar molecule can more easily obtain new functions through modification.
Based on this, developing new compounds by using guar gum and expanding the application range thereof become important research.
Disclosure of Invention
The application aims to provide a guar gum base compound and a preparation method thereof, a zinc-sulfur separation inhibitor and a zinc-sulfur flotation separation method, a flocculating agent and application thereof, so as to solve the problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a guar gum base compound having the general structural formula:
Figure F_210603141613646_646800001
wherein R is1-R9Each independently a hydrogen atom or a functional group capable of chelating a metal ion and R1-R9At least one of which is not H.
Preferably, the functional group capable of chelating with a metal ion is selected from
Figure F_210603141613740_740507002
Figure F_210603141613834_834253003
Figure F_210603141613928_928027004
And
Figure F_210603141614021_021774005
any one of (a);
wherein, L is independently selected from any one of alkyl, aromatic group and heterocyclic group, B is independently selected from any one of O, N, NH and S, A is independently selected from any one of H, alkyl and aryl; x is a positive integer, and y is a positive integer less than or equal to x or zero.
Preferably, each L is independently selected from C1-C6Saturated or unsaturated alkyl of,
Figure F_210603141614115_115549006
Figure F_210603141614209_209287007
And
Figure F_210603141614287_287333008
any one of (a);
wherein a, b, c, d, e and f are independently selected from C, N, O and S.
Preferably, A is selected from H, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-CH(CH2CH3)CH3、-CH(CH2CH3)2、-CH2CH2CH2CH2CH3、-CH(CH2CH2CH3)CH3、-CH2CH2CH2CH2CH2CH3、-CH=CH2、-CH2CH=CH2、-CH2CH2CH=CH2、-CH(CH=CH2)CH3、-C(CH=CH2)(CH3)2、-CH(CH=CH2)CH2CH3、-CH2CH2CH2CH=CH2、-CH(CH2CH3)CH=CH2、-CH=CHCN、-CH2CH2CN、-Ar、-CO-Ar、-CO-R10、-CH2COOM and any one of saturated alkyl acid saturated ester group and saturated alkyl acid unsaturated ester group;
wherein R is10Is selected from C1-C6Saturated or unsaturated alkyl groups; m is a cation.
The present application also provides a method for preparing said guar-based compound comprising:
reacting a compound comprising guar gum and a functional group capable of chelating a metal ion to form the guar base compound.
The present application also provides a zinc-sulfur separation inhibitor comprising the guar-based compound.
The application also provides a zinc-sulfur flotation separation method, which comprises the following steps:
and adding the zinc-sulfur separation inhibitor into ore pulp for flotation.
Preferably, the zinc sulphur flotation separation process satisfies one or more of the following conditions:
a. adding 30-300g of the zinc-sulfur separation inhibitor per ton of the ore pulp;
b. the pH value of the ore pulp is 8-11;
c. before the ore pulp is added, the zinc-sulfur separation inhibitor is prepared into an aqueous solution with the mass concentration of 0.1-1%.
The present application also provides a flocculant comprising the guar-based compound.
The application also provides an application of the flocculant for mineral separation or wastewater treatment.
Compared with the prior art, the beneficial effect of this application includes:
according to the guar gum base compound, guar gum is used as a framework, a polyhydroxy structure in the guar gum structure is utilized, and a functional group capable of chelating metal ions is substituted, so that the guar gum base compound has a good zinc-sulfur separation effect and a good flocculation effect in a flotation process, and has the advantages of good biocompatibility, easiness in biodegradation, simplicity in synthesis, large metal ion chelating adsorption capacity and the like; the synthesis of the guar gum base compound expands the application range of guar gum and can be widely applied to flotation and water treatment processes;
the preparation method of the guar gum base compound provided by the application has the advantages of simple process, low cost and controllable reaction process;
the zinc-sulfur separation inhibitor provided by the application has the advantages of good selectivity and strong inhibition effect by using the guar gum base compound, can effectively reduce the usage amount of alkaline substances in the flotation process, improves the zinc-sulfur separation effect, and further improves the flotation efficiency;
the zinc-sulfur flotation separation method provided by the application is simple in process, and the flotation product grade and the separation recovery rate are high;
the flocculant provided by the application obtains excellent flocculation performance by using the guar gum base compound, and can be applied to the rapid sedimentation process of concentrate or tailings in mineral processing operation, the treatment of mineral processing wastewater and the post-treatment operation procedures of domestic sewage or industrial wastewater containing metal/heavy metal ions and the like.
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To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is an infrared spectrum of the product obtained in example 1;
FIG. 2 is an infrared spectrum of the product obtained in example 3;
figure 3 a process flow diagram of the flotation process provided in example 7;
FIG. 4 shows the results of flotation of pyrite and blende at various inhibitor dosages as provided in example 7;
FIG. 5 is a process flow diagram of the flotation process provided in example 8;
FIG. 6 is a process flow diagram of the flotation process provided in example 9;
FIG. 7 is a schematic view showing changes with time of solid-liquid interfaces in example 12, example 13 and comparative example 5.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A guar gum base compound having the general structural formula:
Figure F_210603141614381_381174009
wherein R is1-R9Each independently a hydrogen atom or a functional group capable of chelating a metal ion and R1-R9At least one of which is not H, n represents the degree of polymerisation, and the molecular weight is typically from 10 to 200 ten thousand.
In an alternative embodiment, the functional group capable of chelating a metal ion is selected from
Figure F_210603141614475_475003010
Figure F_210603141614553_553032011
Figure F_210603141614646_646759012
And
Figure F_210603141614741_741636013
any one of (a);
wherein, L is independently selected from any one of alkyl, aromatic group and heterocyclic group, B is independently selected from any one of O, N, NH and S, A is independently selected from any one of H, alkyl and aryl; x is a positive integer, and y is a positive integer less than or equal to x or zero.
In an alternative embodiment, each of said L is independently selected from C1-C6Saturated or unsaturated alkyl of,
Figure F_210603141614834_834778014
Figure F_210603141614912_912405015
And
Figure F_210603141615021_021785016
any one of (a);
wherein a, b, c, d, e and f are independently selected from C, N, O and S.
In an alternative embodiment, A is selected from H, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-CH(CH2CH3)CH3、-CH(CH2CH3)2、-CH2CH2CH2CH2CH3、-CH(CH2CH2CH3)CH3、-CH2CH2CH2CH2CH2CH3、-CH=CH2、-CH2CH=CH2、-CH2CH2CH=CH2、-CH(CH=CH2)CH3、-C(CH=CH2)(CH3)2、-CH(CH=CH2)CH2CH3、-CH2CH2CH2CH=CH2、-CH(CH2CH3)CH=CH2、-CH=CHCN、-CH2CH2CN、-Ar、-CO-Ar、-CO-R10、-CH2COOM and any one of saturated alkyl acid saturated ester group and saturated alkyl acid unsaturated ester group;
wherein R is10Is selected from C1-C6Saturated or unsaturated alkyl groups; m is a cation.
A method of preparing said guar-based compound comprising:
reacting a compound comprising guar gum and a functional group capable of chelating a metal ion to form the guar base compound.
An inhibitor of zinc-sulfur separation comprising said guar-based compound.
A zinc sulfur flotation separation process comprising:
and adding the zinc-sulfur separation inhibitor into ore pulp for flotation.
In an alternative embodiment, the zinc sulphur flotation separation process satisfies one or more of the following conditions:
a. adding 30-300g of the zinc-sulfur separation inhibitor per ton of the ore pulp;
b. the pH value of the ore pulp is 8-11;
c. before the ore pulp is added, the zinc-sulfur separation inhibitor is prepared into an aqueous solution with the mass concentration of 0.1-1%.
Optionally, the amount of the zinc-sulfur separation inhibitor added per ton of the pulp may be any value between 30g, 50g, 100g, 150g, 200g, 250g, 300g and 30-300 g; the pH value of the ore pulp can be any value between 8, 9, 10, 11 and 8-11; the mass concentration of the aqueous solution of the zinc-sulfur separation inhibitor may be any value between 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, and 0.1% to 1%.
A flocculant comprising the guar-based compound.
The application of the flocculant is used for mineral separation or wastewater treatment.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
This example provides a guar gum base compound having the individual substituents shown in table 1.
This example also provides a method for preparing the guar gum-based compound, which comprises the following steps:
dispersing 1.84 g (0.01 mol) of 2,4, 6-trichloro-1, 3, 5-triazine in water, adding 1.6 g of sodium hydrosulfide (70 percent of effective content) at 0-5 ℃, and reacting for 1 hour at constant temperature; and then heating the system to 30 ℃, and carrying out heat preservation reaction for 2-3 h to obtain the aqueous solution of the intermediate 1. And adding the intermediate 1 into 16.2 g (0.1 mol) of guar gum, heating to 85-90 ℃, reacting for 3 hours at constant temperature, removing the solvent, and drying to obtain a solid product with the substitution degree of 10%. It should be noted that the substitution degree of the final product can be directly calculated according to the charge ratio, and the substitution degree calculation formula is DS% = (n triazine/n guar gum) × 100%; the products with different degrees of substitution can be obtained by adjusting the feeding proportion according to the requirements.
FIG. 1 is an infrared spectrum of the obtained product.
Example 2
This example provides a guar gum base compound having the individual substituents shown in table 1.
This example also provides a method for preparing the guar gum-based compound, which comprises the following steps:
the structure of the embodiment 2 is similar to that of the embodiment 1, only the difference of the feeding is that the specific synthetic steps are as follows: dispersing 3.68 g of 2,4, 6-trichloro-1, 3, 5-triazine in water, adding 3.2 g of sodium hydrosulfide (70 percent of effective content) at 0-5 ℃, and reacting for 1 hour at constant temperature; and then heating the system to 30 ℃, and carrying out heat preservation reaction for 2-3 h. And adding the reactant into 16.2 g of guar gum, heating to 85-90 ℃, reacting for 3 hours at constant temperature, removing the solvent, and drying to obtain a solid product with the substitution degree of 20%. The other guar gum products with different degrees of substitution are prepared by the method according to the equal proportion.
Example 3
This example provides a guar gum base compound having the individual substituents shown in table 1.
This example also provides a method for preparing the guar gum-based compound, which comprises the following steps:
dispersing 1.82 g of 2,4, 6-trichloro-1, 3, 5-triazine in water, adding thiourea (1.52 g, 1.06 g of anhydrous sodium carbonate is added and dissolved in 10 ml of water) at 0-5 ℃, and reacting for 2 hours at constant temperature; then directly heating to 30 ℃ and reacting for about 3 hours to obtain the aqueous solution of the intermediate 2. And adding the intermediate 2 into 16.2 g of guar gum, heating to 85-90 ℃, reacting for 3 hours at constant temperature, removing the solvent, and drying to obtain a solid product.
FIG. 2 is an infrared spectrum of the obtained product.
Example 4
This example provides a guar gum base compound having the individual substituents shown in table 1.
This example also provides a method for preparing the guar gum-based compound, which comprises the following steps:
mixing the intermediates 1 and 2 prepared in the embodiments 1 and 3 according to a ratio of 1:1, adding 16.2 g of guar gum, heating to 85-90 ℃, reacting for 3 hours at constant temperature, removing the solvent, and drying to obtain a solid product. The other guar gum products with different degrees of substitution are prepared by the method according to the equal proportion.
Example 5
This example provides a guar gum base compound having the individual substituents shown in table 1.
This example also provides a method for preparing the guar gum-based compound, which comprises the following steps:
dispersing 1.84 g of 2,4, 6-trichloro-1, 3, 5-triazine in water, adding 1.6 g of sodium hydrosulfide (70 percent of effective content) at 0-5 ℃, and reacting for 1 hour at constant temperature; and then heating the system to 30 ℃, and carrying out heat preservation reaction for 2-3 h. Heating the reaction system to 45 ℃, adding 0.8 g of sodium hydroxide and 1.56 g of carbon disulfide, and reacting at constant temperature for 3 hours to obtain an aqueous solution of an intermediate 3; and adding the intermediate 3 into 16.2 g of guar gum, heating to 85-90 ℃, reacting for 3 hours at constant temperature, removing the solvent, and drying to obtain a solid product.
Example 6
This example provides a guar gum base compound having the individual substituents shown in table 1.
This example also provides a method for preparing the guar gum-based compound, which comprises the following steps:
dispersing 1.84 g of 2,4, 6-trichloro-1, 3, 5-triazine in water, adding 1.6 g of sodium hydrosulfide (70 percent of effective content) at 0-5 ℃, and reacting for 1 hour at constant temperature; and then heating the system to 30 ℃, and carrying out heat preservation reaction for 2-3 h. The reaction system is heated to 45 ℃, 0.8 g of sodium hydroxide and 1.56 g of carbon disulfide are added, and the reaction is carried out for 3 hours at constant temperature until the reaction. Heating to 45 ℃, adding 0.53 g of acrylonitrile, and reacting at constant temperature for 3 hours until an intermediate 4 is obtained; and adding the intermediate 4 into 14.5 g of guar gum, heating to 85-90 ℃, reacting for 3 hours at constant temperature, removing the solvent, and drying to obtain a solid product.
The general formula of the products obtained in examples 1 to 6 is:
Figure F_210603141615181_181064017
the individual substituents of the products obtained in examples 1 to 6 are shown in Table 1:
TABLE 1 substituents corresponding to the respective products
Figure T_210603141616834_834282001
Example 7
The product prepared in example 3 is used as a zinc-sulfur separation inhibitor and applied to the flotation process of pyrite and sphalerite pure minerals, which shows the selective inhibition effect on pyrite (the mineral sources are 46.15% of iron in some delafossite in Hunan, 51.77% of sulfur, 65.68% of zinc in some sphalerite in Guangxi, 32.46% of sulfur, and the purity of the minerals is more than 97% through chemical multi-element analysis and XRD test).
The process flow diagram is shown in fig. 3, and the specific flotation process is as follows:
adjusting the pH value of the ore pulp to 8-10 by using sodium hydroxide, and sequentially adding 1 multiplied by 10 copper sulfate-6mol/L, 20 mg/L of zinc-sulfur separation inhibitor, and finally adding 20 mg/L of collector isobutyl xanthate and 25mg/L of foaming agent MIBC (methyl isobutyl carbinol).
The flotation results of pyrite and blende with different amounts of depressants are shown in fig. 4, and it can be seen from fig. 4 that the recovery of pyrite was 24.15% and the recovery of blende was 83.07% using the guar-based compound obtained in example 3 as the depressants. The inhibitor provided by the application has good selection performance.
Example 8
The product prepared in the example 3 is used as a zinc-sulfur separation inhibitor and applied to lead-zinc ore flotation separation.
The ore is selected from certain lead-zinc sulfide ore in Jiangsu, wherein the lead grade in the raw ore is 4.25%, the zinc grade is 6.62%, and the sulfur grade is 28.95%, while the lead mineral is mainly galena, the zinc mineral is mainly sphalerite, the sulfur mineral is mainly pyrite, and the gangue mineral is mainly quartz, calcite, dolomite and muscovite.
The flotation process flow is shown in fig. 5, and the detailed test process and the medicament system are as follows: the ore roughing grinding fineness is 70 percent, the lime is 800 g/t, the sodium sulfide is 200g/t, the ore is added into a grinding machine, the pulp adjusting concentration is about 30 percent, the zinc sulfate is 1000g/t, the sodium sulfite is 1000g/t, the aniline black powder is 60 g/t, the BK204 foaming agent is 12g/t, and lead roughing and lead scavenging are carried out; then adding lime (calcium oxide) 500g/t and the inhibitor obtained in example 3 100 g/t, copper sulfate 200g/t, isobutyl xanthate 80 g/t, BK204 foaming agent 4 g/t, and obtaining zinc rough concentrate through one-time rough concentration, wherein the obtained results are as follows: the zinc grade in the zinc rough concentrate is 27.47 percent, and the recovery rate is 97.71 percent.
Comparative example 1
In contrast to example 8, 1500g/t lime was added after lead roughing and lead scavenging, and the inhibitor obtained in example 3 was not added.
The zinc grade in the obtained zinc rough concentrate is 19.82 percent, and the recovery rate is 96.75 percent.
Comparative example 2
In contrast to example 8, 2000g/t lime was added after lead roughing and lead scavenging, without addition of the inhibitor obtained in example 3.
The zinc grade in the zinc rough concentrate is 22.39 percent, and the recovery rate is 97.67 percent.
The flotation results of example 8 and comparative examples 1 and 2 show that the inhibitor provided by the application has better inhibition selectivity, and can obviously reduce the addition amount of lime.
Example 9
The product obtained in example 3 is applied to the separation and flotation process of lead-zinc sulfide ore of inner Mongolia, lead grade in raw ore is 2.02%, zinc grade is 2.40%, and sulfur grade is 6.57%, wherein lead mineral mainly is galena, zinc mineral mainly is sphalerite, sulfur mineral mainly is pyrite and a small amount of pyrrhotite, gangue mineral mostly is quartz, and then muscovite, a small amount of chlorite, albite, calcite, potash feldspar and the like.
The flotation process flow is shown in figure 6, and the detailed flotation reagent dosage and operation conditions are as follows: the ore roughing and grinding fineness is 75 percent of-200 meshes, lime is added into a grinding machine at 2000g/t, the pulp mixing concentration is about 30 percent, zinc sulfate is added at 1500g/t, sodium sulfite is 1000g/t, ethidium and nitrogen are 50 g/t, ammonium nitrate is 20 g/t, and a BK204 foaming agent is 16 g/t, and lead roughing and lead scavenging are carried out; then lime or the inhibitor described in the embodiment 2 of the invention, 100 g/t of copper sulfate, 60 g/t of isobutyl xanthate and 10 g/t of BK204 foaming agent are added, and zinc rough concentrate is obtained through one-time rough concentration, and the obtained results are as follows: in the zinc flotation operation, lime 200g/t and the inhibitor 50 g/t obtained in example 3 are used in combination to obtain the zinc level in the zinc rough concentrate of 26.33 percent, and the recovery rate is 89.11 percent.
Comparative example 3
In contrast to example 9, the zinc flotation was carried out with the addition of 1000g/t lime and without the addition of the depressants obtained in example 3.
The zinc grade in the zinc rough concentrate is 19.09 percent, and the recovery rate is 90.51 percent.
Comparative example 4
In contrast to example 9, the zinc flotation was carried out with the addition of 2000g/t lime and without the addition of the depressants obtained in example 3.
The zinc grade in the obtained zinc rough concentrate is 25.11 percent, and the recovery rate is 89.64 percent.
The flotation results of example 9 and comparative examples 3 and 4 show that the inhibitor provided by the application has better inhibition selectivity, and can obviously reduce the addition amount of lime.
Examples 10 to 11
The products of example 1 and example 3 were applied to a chelating flocculation process of lead ions to illustrate their chelating effect on heavy metal ions.
The detailed experimental procedure is as follows: the concentration of the preparation is 1 x 10-3A lead ion solution (0.2 g/L) was added in an amount of 50 mL, and then 0.15g of each of the products obtained in examples 1 and 3 was added thereto, and the mixture was stirred sufficiently, allowed to stand, and then the lead ion concentration in the supernatant was analyzed. Tested to obtain IIThe lead ion concentration of the lead ion is 0.031 g/L and 0.044 g/L respectively; the lead ion removal rates of examples 1 and 3 were 84.5% and 78.0%, respectively, indicating that the guar-based compounds (guar-based chelating flocculants) obtained herein have good ion chelating effects.
Examples 12 to 13
The products obtained in example 1 and example 3 are taken as examples and applied to the flocculation of copper ore dressing tailings of certain copper ores in Hubei, and the flocculation effect of the products on actual ore pulp is illustrated.
The specific test procedures are as follows: accurately transferring 300 mL of copper-selecting tailing pulp with the mass concentration of 10%, filling the pulp into a 500 mL beaker, uniformly stirring the pulp at 150 rpm by using electronic constant-speed stirring, adding a flocculating agent (products obtained in example 1 and example 3) according to the amount of 10 mg/L, and then stirring the pulp at 300 rpm for 2 min; and then stirring at a low speed of 80 rpm for 5 min, finally transferring the ore pulp into a measuring cylinder, and recording the height values of the solid-liquid interface at different times.
Comparative example 5
Unlike example 12 and example 13, no flocculant was added.
The measurement results are shown in fig. 7. As can be seen from fig. 7, the settling rate of the pulp after the flocculant is added is significantly faster than that of the flocculant-free group, which indicates that the guar-based chelating flocculant provided by the present application has a good flocculation effect.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (6)

1. A method of preparing a guar-based compound, wherein the guar-based compound has the general structural formula:
Figure F_210906165020601_601013001
wherein R is1-R9Each independently a hydrogen atom or a functional group capable of chelating a metal ion and R1-R9At least one of which is not H;
the functional group capable of chelating with a metal ion is selected from
Figure F_210906165020712_712849002
Figure F_210906165020806_806877003
Figure F_210906165020918_918147004
And
Figure F_210906165021058_058106005
any one of (a);
wherein, L is independently selected from any one of alkyl, aromatic group and heterocyclic group, B is independently selected from any one of O, N, NH and S, A is independently selected from any one of H, alkyl and aryl; x is a positive integer, y is a positive integer less than or equal to x or zero;
the preparation method comprises the following steps:
reacting a compound comprising guar gum and a functional group capable of chelating a metal ion to form the guar base compound.
2. The method of preparing a guar gum-based compound according to claim 1, characterized in that each L is independently selected from C1-C6Saturated or unsaturated alkyl of,
Figure F_210906165021169_169931006
Figure F_210906165021299_299737007
And
Figure F_210906165021424_424176008
any one of (a);
wherein a, b, c, d, e and f are independently selected from C, N, O and S.
3. Method for preparing a guar-based compound according to claim 1 or 2, characterized in that a is selected from H, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3、-CH2CH(CH3)2、-CH(CH2CH3)CH3、-CH(CH2CH3)2、-CH2CH2CH2CH2CH3、-CH(CH2CH2CH3)CH3、-CH2CH2CH2CH2CH2CH3、-CH=CH2、-CH2CH=CH2、-CH2CH2CH=CH2、-CH(CH=CH2)CH3、-C(CH=CH2)(CH3)2、-CH(CH=CH2)CH2CH3、-CH2CH2CH2CH=CH2、-CH(CH2CH3)CH=CH2、-CH=CHCN、-CH2CH2CN、-Ar、-CO-Ar、-CO-R10、-CH2COOM and any one of saturated alkyl acid saturated ester group and saturated alkyl acid unsaturated ester group;
wherein R is10Is selected from C1-C6Saturated or unsaturated alkyl groups; m is a cation.
4. A zinc-sulfur flotation separation method is characterized by comprising the following steps:
adding a zinc-sulfur separation inhibitor into ore pulp for flotation;
the inhibitor of zinc-sulfur separation comprises a guar-based compound prepared by the method of making a guar-based compound according to any one of claims 1-3.
5. The zinc sulphur flotation separation process according to claim 4, wherein one or more of the following conditions are met:
a. adding 30-300g of the zinc-sulfur separation inhibitor per ton of the ore pulp;
b. the pH value of the ore pulp is 8-11;
c. before the ore pulp is added, the zinc-sulfur separation inhibitor is prepared into an aqueous solution with the mass concentration of 0.1-1%.
6. The application of the flocculant is characterized in that the flocculant is used for mineral separation or wastewater treatment;
the flocculant comprises a guar-based compound prepared by the method of any one of claims 1 to 3.
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