Columnar activated carbon prepared using hazardous waste resources from pharmaceutical factories, preparation method thereof, and application thereof

Abstract

The present invention belongs to the technical field of activated carbon preparation. In order to solve the problem that the saturated powdered activated carbon and sulfur red mother liquor residue used in pharmaceutical factories are difficult to be reused and harmlessly treated, a columnar activated carbon prepared by using hazardous waste resources of pharmaceutical factories and a preparation method and application thereof are provided. Phosphoric acid is added to the saturated powdered activated carbon adsorbed by hazardous waste resources of pharmaceutical factories after drying, and the material is trapped in the silo for 24 hours to make the phosphoric acid and saturated powdered activated carbon fully react; continue drying, add sulfur red mother liquor residue, binder, and modified asphalt to the dried saturated powdered activated carbon to make strips, dry, carbonize at 760°C for 60 minutes, activate with water vapor at 860°C for 120 minutes, and cool to obtain columnar activated carbon. The reuse and harmless treatment of saturated powdered activated carbon (hereinafter referred to as saturated powdered activated carbon) and sulfur red mother liquor residue adsorbed by pharmaceutical factories can be realized. The prepared columnar activated carbon is suitable for the adsorption of VOC gas and the adsorption of COD in sewage.

Description

Technical Field

[0001] The invention belongs to the technical field of activated carbon preparation, and specifically relates to columnar activated carbon prepared by utilizing hazardous waste resources of a pharmaceutical factory, and a preparation method and application thereof. Background Art

[0002] Activated carbon is a porous adsorbent widely used in petroleum, chemical, food, medicine, light industry, environmental protection, national defense, etc. The raw materials for making activated carbon are varied, and commonly used ones include wood, coal, fruit shells, waste tires, etc.

[0003] Saturated powdered activated carbon (hereinafter referred to as saturated powdered activated carbon) after use in pharmaceutical factories is a hazardous waste in the pharmaceutical industry. It is generally a wet material. If it is piled up for a long time without treatment, it is very easy to cause great pollution to the environment. Because saturated activated carbon contains a large amount of antibiotics, etc., it cannot be landfilled or piled up. The existing treatment method for saturated powdered activated carbon is only incineration. However, saturated powdered activated carbon has a low calorific value and is difficult to burn. It is an underutilized hazardous waste resource with broad development prospects. Therefore, realizing the resource reuse and harmless treatment of saturated powdered activated carbon can not only protect the environment, but also improve the utilization rate of resources.

[0004] Erythromycin thiocyanate crystallization mother liquor precipitate (hereinafter referred to as sulfur red mother liquor slag) is the precipitate produced in the mother liquor after erythromycin thiocyanate is crystallized from the reaction mother liquor during the production process of erythromycin thiocyanate; it is an intermediate product in the production of erythromycin thiocyanate. Sulfur red mother liquor slag is a viscous substance rich in refractory organic matter and biotoxic substances and a chemical synthesis waste product. Sulfur red mother liquor slag contains high chemical oxygen demand, i.e. high COD, high ammonia nitrogen and high suspended solids, i.e. high SS, from fermentation residual nutrients; there are biological inhibitory substances, such as residual erythromycin and its intermediate metabolites, SCN-, high concentration of sulfate, surfactant (demulsifier, defoamer, etc.) and high concentration of acid, alkali, organic solvent, etc. remaining in extraction and separation. At present, the only treatment method for sulfur red mother liquor slag is incineration. Due to its low calorific value, it can only be mixed with coal for combustion. It is an underutilized hazardous waste resource with broad development prospects. Therefore, the resource recycling and harmless treatment of sulfur red mother liquor slag can not only protect the environment, but also improve the utilization rate of resources. Summary of the invention

[0005] In order to solve the problem that the saturated powdered activated carbon and sulfur red mother liquor residue after use are difficult to be reused and harmlessly treated in pharmaceutical factories, the present invention provides a columnar activated carbon prepared by using hazardous waste resources of pharmaceutical factories and a preparation method and application thereof. The saturated powdered activated carbon and sulfur red mother liquor residue adsorbed by pharmaceutical factories can be reused and harmlessly treated. The high temperature in the production process of the columnar activated carbon can decompose harmful substances such as antibiotics and residual nutrients in the saturated powdered activated carbon and sulfur red mother liquor residue at high temperature, and the smoke after decomposition is incinerated.

[0006] The present invention is achieved by the following technical scheme: a preparation method of columnar activated carbon prepared by utilizing hazardous waste resources of pharmaceutical factories, wherein saturated powdered activated carbon adsorbed by hazardous waste resources of pharmaceutical factories is dried, and then phosphoric acid is added in a mass ratio of 1:1, and then the material is trapped in a silo for 24 hours to allow the phosphoric acid and saturated powdered activated carbon to fully react; the saturated powdered activated carbon is further dried, and erythromycin thiocyanate crystal mother liquor precipitate, i.e., sulfur red mother liquor slag, a binder, and modified asphalt are added to the dried saturated powdered activated carbon, and then made into strips, dried to a water content of ≤6%, and then carbonized at 760°C for 60 minutes, activated by steam at 860°C for 120 minutes, and columnar activated carbon is obtained after cooling; wherein the mass fractions of saturated powdered activated carbon, sulfur red mother liquor slag, modified asphalt, and binder are 61-76%, 0-15%, 19%, and 5%, respectively.

[0007] The specific preparation method is:

[0008] (1) Pretreatment of saturated powdered activated carbon: Dry the saturated powdered activated carbon in a double-shaft dryer at 160°C for 30 minutes to evaporate the water in the saturated powdered activated carbon for later use;

[0009] (2) Adding acid: Add phosphoric acid in proportion to the dried saturated powdered activated carbon in a drum mixer to fully blend the phosphoric acid into the saturated powdered activated carbon;

[0010] (3) Material entrapment: The material is trapped in a stainless steel silo for 24 hours to allow phosphoric acid to fully react with saturated powdered activated carbon;

[0011] (4) Drying: Drying in a double-shaft dryer at 160°C for 40 min to evaporate the water in the saturated powdered activated carbon soaked in phosphoric acid;

[0012] (5) Molding: Add sulfur red mother liquor residue, binder and modified asphalt to the dried saturated powdered activated carbon in proportion, knead it into a paste with a kneader, and press it into strips with a hydraulic press;

[0013] (6) Carbonization: Use a steam dryer to dry the pressed strip material to a moisture content of ≤6%, and then send it into an externally heated carbonization furnace for carbonization at 760°C for 60 minutes;

[0014] (7) Activation: After carbonization is completed, the material is sent to the activation furnace for activation at 860°C with steam for 120 minutes, and the activated material is discharged;

[0015] (8) Cooling: The activated material becomes columnar activated carbon after natural cooling.

[0016] The saturated powdered activated carbon is a mixture of saturated powdered activated carbon for decolorization, saturated powdered activated carbon for solvent, and saturated powdered activated carbon for adsorbing phenylacetic acid. The mass of the saturated powdered activated carbon is used as the calculation basis, and the saturated powdered activated carbon for decolorization, saturated powdered activated carbon for solvent, and saturated powdered activated carbon for adsorbing phenylacetic acid are mixed according to the following mass fractions: 69%, 28%, and 3%.

[0017] The binder is starch, borax, sodium tripolyphosphate, sodium hexametaphosphate and butanediol. Taking the final mass of the binder as a calculation basis, the mass fractions of starch, borax, sodium tripolyphosphate, sodium hexametaphosphate and butanediol are 68%, 13%, 3%, 3% and 13% respectively.

[0018] Furthermore, the mass fractions of the saturated powdered activated carbon, sulfur red mother liquor slag, modified asphalt and binder are 61%, 15%, 19% and 5% respectively.

[0019] After natural cooling, the activated carbon is screened and packaged. The diameter of the columnar activated carbon is 4mm. The flue gas in the carbonization and activation process is incinerated at high temperature and then discharged.

[0020] The invention also provides columnar activated carbon, which is prepared by the method.

[0021] The present invention also provides the application of the columnar activated carbon in VOC gas adsorption and the application of the columnar activated carbon in COD adsorption in sewage.

[0022] The invention solves the problem that the saturated powdered activated carbon and sulfur red mother liquor residue after use in the existing pharmaceutical factories cannot be recycled and harmlessly treated. The production process is simple, and the large-scale treatment of hazardous wastes of saturated activated carbon and sulfur red mother liquor residue can be achieved, and the invention is easy to promote and apply. At the same time, the iodine value of the prepared columnar activated carbon is 650 mg / g (measured by GB / T7702.7-2008), the ash content is 24% (measured by GB / T7702.15-2008), and the wear resistance is 95% (measured by GB / T7702.3-2008). The obtained columnar activated carbon is suitable for the adsorption of VOC gases and the adsorption of COD in sewage. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0024] Figure 1 It is saturated powdered activated carbon after adsorption of phenylacetic acid; Figure 2 Saturated powdered activated carbon for decolorization; Figure 3 It is sulfur red mother liquor slag; Figure 4 To provide proportioned ingredients and kneading diagrams; Figure 5 Drying for granulation; Figure 6 It is a carbonization and activation equipment; Figure 7 The prepared finished columnar activated carbon. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0026] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the disclosure and materials cited therein are hereby incorporated by reference.

[0027] Technical equivalents to the specific embodiments described that are apparent to those skilled in the art using no more than routine experimentation are intended to be encompassed by this application.

[0028] The experimental methods in the following examples are conventional methods unless otherwise specified. The instruments and equipment used in the following examples are conventional laboratory instruments and equipment unless otherwise specified; the experimental materials used in the following examples are purchased from conventional biochemical reagent stores unless otherwise specified.

[0029] Embodiment 1: A method for preparing columnar activated carbon using hazardous waste resources from pharmaceutical factories, wherein saturated powdered activated carbon adsorbed from hazardous waste resources from pharmaceutical factories is dried, phosphoric acid is added in a mass ratio of 1:1, and then the material is trapped in a silo for 24 hours to allow the phosphoric acid and saturated powdered activated carbon to fully react; the saturated powdered activated carbon is further dried, and erythromycin thiocyanate crystal mother liquor precipitate, i.e., sulfur red mother liquor slag, a binder, and modified asphalt are added to the dried saturated powdered activated carbon, wherein the saturated powdered activated carbon, sulfur red mother liquor slag, modified asphalt, and the binder are in a mass ratio of 61:15:19:5; then the strips are made and dried to a moisture content of ≤6%, and then carbonized at 760°C for 60 minutes, activated by steam at 860°C for 120 minutes, and cooled to obtain columnar activated carbon;

[0030] The specific steps are as follows:

[0031] (1) Pretreatment of saturated powdered activated carbon: Dry the saturated powdered activated carbon in a double-shaft dryer at 160°C for 30 minutes to evaporate the water in the saturated powdered activated carbon for later use;

[0032] (2) Adding acid: Add phosphoric acid to the dried saturated powdered activated carbon in a drum mixer at a mass ratio of 1:1, so that the phosphoric acid is fully integrated into the saturated powdered activated carbon;

[0033] (3) Material entrapment: The material is trapped in a stainless steel silo for 24 hours to allow phosphoric acid to fully react with saturated powdered activated carbon;

[0034] (4) Drying: Drying in a double-shaft dryer at 160°C for 40 min to evaporate the water in the saturated powdered activated carbon soaked in phosphoric acid;

[0035] (5) Molding: Add sulfur red mother liquor residue, binder and modified asphalt to the dried saturated powdered activated carbon, knead it into a paste with a kneader, and press it into 4 mm strips with a hydraulic press;

[0036] The binder is starch, borax, sodium tripolyphosphate, sodium hexametaphosphate, and butanediol, with a mass ratio of 68:13:3:3:13;

[0037] (6) Carbonization: Use a steam dryer to dry the pressed strip material to a moisture content of ≤6%, and then send it into an externally heated carbonization furnace for carbonization at 760°C for 60 minutes;

[0038] (7) Activation: After carbonization is completed, the material is sent to the activation furnace for activation at 860°C with steam for 120 minutes, and the activated material is discharged;

[0039] (8) Cooling: The activated material is naturally cooled, sieved and packaged to make 4mm columnar activated carbon; the carbonized and activated flue gas is incinerated at high temperature and then discharged.

[0040] Among them: saturated powdered activated carbon includes saturated powdered activated carbon for decolorization, saturated powdered activated carbon for solvent, and saturated powdered activated carbon for adsorbing phenylacetic acid, with a mass ratio of 69:28:3.

[0041] The obtained columnar activated carbon was tested for iodine value using GB / T7702.7-2008, ash content using GB / T7702.15-2008, and abrasion resistance using GB / T7702.3-2008. After testing: the iodine value of the prepared columnar activated carbon is 654mg / g, the ash content is 24%, and the abrasion resistance is 96.34%. This activated carbon is suitable for the adsorption of VOC gas and COD in sewage. The performance analysis test results of the obtained materials are shown in Table 1.

[0042] Table 1

[0043]

[0044] Example 2: A method for preparing columnar activated carbon using hazardous waste resources from a pharmaceutical factory, wherein the mass fractions of saturated powdered activated carbon, modified asphalt and binder are 76%, 19% and 5%, respectively. The remaining methods are the same as those described in Example 1.

[0045] Example 3: A method for preparing columnar activated carbon using hazardous waste resources from a pharmaceutical factory, wherein the mass fractions of saturated powdered activated carbon, sulfur red mother liquor residue, modified asphalt and binder are 70%, 6%, 19% and 5%, respectively. The rest of the method is the same as that described in Example 1.

[0046] Experimental Example 1: Screening experiment of raw material ratio of columnar activated carbon:

[0047] Twinings decolorized powdered carbon, Twinings solvent powdered carbon (smell), Twinings phenylacetic acid powdered carbon (smellless), modified asphalt, sulfur red mother liquor residue, and binder were mixed in the proportions shown in Table 2 to prepare columnar activated carbon, and then the activation strength, activated bulk weight, iodine value, ash content, and volatile matter were tested. The test results of the prepared materials are shown in Table 3. All experiments were pressed into 4 mm.

[0048] Table 2

[0049]

[0050] Table 3

[0051]

[0052] Combined with the test results in Table 3, when the content of sulfur red mother liquor is too high, no matter how high the asphalt content is or how much binder is added, granulation is impossible, either it cannot be formed, or the carbonization strength is poor, all of them are powders, and granulation is impossible. When sulfur red mother liquor is not added, the activation strength and activation pile weight of the granulation are improved, but the iodine value decreases, and the ash and volatile content decreases. When the content of sulfur red mother liquor accounts for 15%, the activation strength and activation pile weight increase, the iodine value increases, and the ash and volatile content increase relatively, which can fully meet the national standards and is suitable for the adsorption of VOC gases and the adsorption of COD in sewage. When the asphalt content is too high, no matter how high the binder content is, the resulting material has poor activation strength after molding, low pile weight, and is not conducive to the adsorption of pollutants.

[0053] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing columnar activated carbon using hazardous waste resources from pharmaceutical factories, characterized in that: After drying, add phosphoric acid in a mass ratio of 1:1 to the saturated powdered activated carbon for hazardous waste resource adsorption in pharmaceutical factories, and then store the material in the silo for 24 hours to allow the phosphoric acid and saturated powdered activated carbon to fully react; continue to dry the saturated powdered activated carbon, add erythromycin thiocyanate crystal mother liquor precipitate, i.e., sulfur red mother liquor slag, binder, and modified asphalt to the dried saturated powdered activated carbon, and then make it into strips, dry it to a moisture content of ≤6%, and then carbonize it at 760°C for 60 minutes, activate it with water vapor at 860°C for 120 minutes, and cool it to obtain columnar activated carbon; The mass fractions of saturated powdered activated carbon, sulfur red mother liquor slag, modified asphalt and binder are 61%, 15%, 19% and 5% respectively; The saturated powdered activated carbon is a mixture of saturated powdered activated carbon for decolorization, saturated powdered activated carbon for solvent, and saturated powdered activated carbon for adsorption of phenylacetic acid. The mass of the saturated powdered activated carbon is used as the calculation basis. The saturated powdered activated carbon for decolorization, the saturated powdered activated carbon for solvent, and the saturated powdered activated carbon for adsorption of phenylacetic acid are mixed according to the following mass fractions: 69%, 28%, and 3%; The binder is starch, borax, sodium tripolyphosphate, sodium hexametaphosphate and butanediol. Taking the final mass of the binder as a calculation basis, the mass fractions of starch, borax, sodium tripolyphosphate, sodium hexametaphosphate and butanediol are 68%, 13%, 3%, 3% and 13% respectively.

2. The method for preparing columnar activated carbon using hazardous waste resources from pharmaceutical factories according to claim 1, characterized in that: The specific preparation method is: (1) Pretreatment of saturated powdered activated carbon: Dry the saturated powdered activated carbon in a double-shaft dryer at 160°C for 30 minutes to evaporate the water in the saturated powdered activated carbon for later use; (2) Adding acid: Add phosphoric acid in proportion to the dried saturated powdered activated carbon in a drum mixer to fully blend the phosphoric acid into the saturated powdered activated carbon; (3) Material entrapment: The material is trapped in a stainless steel silo for 24 hours to allow phosphoric acid to fully react with saturated powdered activated carbon; (4) Drying: Drying in a double-shaft dryer at 160°C for 40 min to evaporate the water in the saturated powdered activated carbon soaked in phosphoric acid; (5) Molding: Add sulfur red mother liquor residue, binder and modified asphalt to the dried saturated powdered activated carbon in proportion, knead it into a paste with a kneader, and press it into strips with a hydraulic press; (6) Carbonization: Use a steam dryer to dry the pressed strip material to a moisture content of ≤6%, and then send it into an externally heated carbonization furnace for carbonization at 760°C for 60 minutes; (7) Activation: After carbonization is completed, the material is sent to the activation furnace for activation at 860°C with steam for 120 minutes, and the activated material is discharged; (8) Cooling: The activated material becomes columnar activated carbon after natural cooling.

3. The method for preparing columnar activated carbon using hazardous waste resources from pharmaceutical factories according to claim 2, characterized in that: After natural cooling, the activated carbon is screened and packaged. The diameter of the columnar activated carbon is 4 mm.

4. The method for preparing columnar activated carbon using hazardous waste resources from pharmaceutical factories according to claim 2, characterized in that: The flue gas in the carbonization and activation process is incinerated at high temperature and then discharged.

5. A columnar activated carbon prepared by the method according to claim 1 or 2.

6. Use of the columnar activated carbon according to claim 5 in VOC gas adsorption.

7. Use of the columnar activated carbon according to claim 5 in the adsorption of COD in sewage.

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