Hydrogen peroxide decarburization technology and adsorption material regeneration method thereof
By using specific adsorbent materials and extrusion regeneration technology, the problem of excessive organic carbon content in hydrogen peroxide production has been solved, achieving efficient and safe decarbonization of hydrogen peroxide, reducing production costs and wastewater volume, and improving the operational stability of the equipment.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-05
- Publication Date
- 2026-03-10
AI Technical Summary
The existing hydrogen peroxide production process has an excessively high organic carbon content, which affects the activity of the catalyst and the equipment, leading to equipment blockage and a decrease in product purity. Traditional decarbonization processes have problems such as high consumption, complex operation, and large wastewater volume.
Adsorption treatment is carried out using specific types of adsorbent materials such as polyvinyl alcohol, polyester, polyurethane and other elastic materials, combined with extrusion regeneration technology, to control the total carbon mass concentration difference ≥30ppm and reduce the organic carbon content.
It achieves efficient, safe and environmentally friendly hydrogen peroxide decarbonization, reduces production costs, reduces wastewater generation, simplifies regeneration operations, and improves the stability of equipment operation.
Smart Images
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of organic carbon removal of hydrogen peroxide, in particular to a hydrogen peroxide decarburization technology, a regeneration method of adsorption material thereof and a finished hydrogen peroxide. BACKGROUND
[0002] Hydrogen peroxide is widely used in the synthesis of industrial products, papermaking, environmental protection, food and medicine industries as a basic green chemical raw material. Industrial-grade hydrogen peroxide will bring a large amount of organic matter in the production process, resulting in too high total organic carbon content, such as production raw materials (anthraquinone), organic solvents (trioctyl phosphate, heavy aromatic hydrocarbons, tetrabutyl urea) and their decomposition products, among which the main one is anthraquinone.
[0003] In recent years, with the development and application of caprolactam, propylene oxide, epichlorohydrin and other chemical synthesis technologies and the continuous expansion of their scale, the application range and demand of hydrogen peroxide are increasing, and the production scale of the supporting hydrogen peroxide device is also increasing. If hydrogen peroxide with too high organic carbon is used for large-scale production, it will bring this part of organic matter into the production process, affecting the activity of the catalyst, easily blocking the device equipment and pipelines, and affecting the final refining and product purity of the product.
[0004] At present, the mainstream decarburization process of hydrogen peroxide includes coalescence separation, large particle resin adsorption and extraction. Taking the extraction method of a device as an example, heavy aromatic hydrocarbons are used to extract dilute hydrogen peroxide, and the aromatic hydrocarbons are used to prepare the working solution after the extraction of aromatic hydrocarbons is saturated. The aromatic hydrocarbons used for removing total carbon become "single" consumption, and the consumption of aromatic hydrocarbons in the device is large. In order to ensure the decarburization effect, the total amount of working solution in the device is increasing, which is not conducive to the operation of the device. Coalescence separation must be two-phase separation, and the separation effect of single-phase hydrogen peroxide solution is limited. After large particle adsorption is saturated, water and methanol are needed for regeneration, which has the disadvantages of high regeneration operation frequency, complex operation and large amount of waste water (about 250 kg of regeneration waste water per ton of hydrogen peroxide).
[0005] Therefore, it is necessary to develop a safe, efficient and low-waste hydrogen peroxide decarburization process. SUMMARY
[0006] The purpose of the present application is to provide an efficient, safe and environmentally friendly hydrogen peroxide decarburization method.
[0007] In order to achieve the above purpose, the first aspect of the present application provides a hydrogen peroxide decarburization technology and a regeneration method of adsorption material thereof, which comprises:
[0008] The raw material hydrogen peroxide flows through the adsorption material for adsorption treatment to obtain finished hydrogen peroxide; the control conditions are such that the difference between the total carbon mass concentration c1 of the raw material hydrogen peroxide and the total carbon mass concentration c2 of the finished hydrogen peroxide satisfies: c1-c2≥30ppm;
[0009] The adsorbent material is selected from at least one of the original adsorbent material and the nth regenerated adsorbent material; where n is an integer ≥1; when n=1, the nth regenerated adsorbent material is obtained by extrusion regeneration of the original adsorbent material; when n≥2, the nth regenerated adsorbent material is obtained by extrusion regeneration of (n-1)th regenerated adsorbent material.
[0010] The original adsorbent material is an elastic material, selected from at least one of polyvinyl alcohol, polyester, polyurethane, and polyether materials, and has a density of 16-60 kg / m³. 3 .
[0011] The second aspect of the present invention provides a finished hydrogen peroxide product prepared by the method described in the first aspect above.
[0012] The decarbonization method for hydrogen peroxide provided by this invention employs specific types and conditions of adsorbent materials. The raw hydrogen peroxide to be treated is passed through the adsorbent material, effectively reducing the total carbon content. This invention utilizes novel adsorbent materials in the decarbonization process of hydrogen peroxide. Compared to traditional macroporous adsorption resins, it significantly reduces production costs, offers simple, safe, and reliable regeneration, generates less waste, and demonstrates promising application prospects.
[0013] The adsorbent material provided by this invention is suitable for desorption treatment by extrusion regeneration, which is not only simple to operate, but also reduces energy consumption, saves costs, reduces wastewater generation and the use of organic desorbents, and is more energy-efficient and environmentally friendly. Detailed Implementation
[0014] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0015] In this invention, the total carbon content (TOC) in hydrogen peroxide refers to the content of organic matter in hydrogen peroxide, and this invention does not have any particular restrictions on the type and source of such organic matter.
[0016] As previously described, the first aspect of the present invention provides a hydrogen peroxide decarbonization technology and a method for regenerating the adsorbent material thereof, the method comprising:
[0017] The raw hydrogen peroxide is passed through an adsorption material for adsorption treatment to obtain the finished hydrogen peroxide; the control conditions are such that the difference between the total carbon mass concentration c1 of the raw hydrogen peroxide and the total carbon mass concentration c2 of the finished hydrogen peroxide satisfies: c1-c2≥30ppm.
[0018] The adsorbent material is selected from at least one of the original adsorbent material and the nth regenerated adsorbent material; where n is an integer ≥1; when n=1, the nth regenerated adsorbent material is obtained by extrusion regeneration of the original adsorbent material; when n≥2, the nth regenerated adsorbent material is obtained by extrusion regeneration of (n-1)th regenerated adsorbent material.
[0019] The original adsorbent material is an elastic material, selected from at least one of polyvinyl alcohol, polyurethane, and polyether materials, and has a density of 16-60 kg / m³. 3 .
[0020] In a preferred embodiment, the control conditions ensure that the difference between the total carbon concentration c1 of the raw hydrogen peroxide and the total carbon concentration c2 of the finished hydrogen peroxide satisfies: c1-c2≥60ppm; more preferably, it satisfies 70ppm≤c1-c2≤120ppm. The inventors discovered in their research that by controlling the conditions, the total carbon concentration in the raw hydrogen peroxide can be significantly reduced. The adsorption material provided by this invention has the advantages of high adsorption efficiency and easy regeneration.
[0021] Preferably, n is an integer from 1 to 5, and more preferably an integer from 1 to 3.
[0022] Preferably, the original adsorbent material is polyurethane.
[0023] Preferably, the density of the original adsorbent material is 28-50 kg / m³. 3 More preferably, the original adsorbent material is polyurethane with a density of 28-50 kg / m³. 3 The inventors discovered in their research that using the adsorbent material under these optimized conditions to decarbonize the raw hydrogen peroxide results in higher treatment efficiency. The regenerated adsorbent material obtained after extrusion regeneration has even better treatment capacity, leading to a finished hydrogen peroxide product with lower total carbon content and better stability.
[0024] The present invention does not impose any particular limitation on the shape of the adsorbent material. For example, it can be a cylinder, a cube, a cuboid, a sphere, etc. The present invention will not be described in detail here, and those skilled in the art should not understand it as a limitation of the present invention.
[0025] In this invention, the adsorbent material used in the adsorption treatment can be a single unit or a combination of multiple adsorbent materials. Preferably, this invention uses a single unit of adsorbent material for the adsorption treatment. The inventors have found that under this preferred condition, the treatment efficiency of the hydrogen peroxide is higher, and the operation is simpler.
[0026] In a preferred embodiment, the volume compression ratio of the extrusion regeneration process is 1-5:10.
[0027] The volume compression ratio mentioned in this invention refers to the ratio of the volume of the adsorbent material after compression to the volume before compression. The compression regeneration process described in this invention involves desorbing the adsorbent material containing organic matter by compression under external force. The adsorbent material provided by this invention is elastic, and after the external force is removed, the volume of the regenerated adsorbent material will gradually recover to a level comparable to the original adsorbent material, rather than remaining in the compressed state indefinitely.
[0028] In the preferred case, n=1, and the processing capacity of the regenerated adsorbent material is 80-95% of that of the original adsorbent material.
[0029] In the preferred case, n≥2, the processing capacity of the adsorbent material after n regenerations is 80-90% of that after (n-1) regenerations.
[0030] In this invention, the "processing capacity" of the adsorbent material refers to the difference between the total carbon content of the treated hydrogen peroxide and the total carbon content of the raw hydrogen peroxide when the same volume of the original adsorbent material or the n-times regenerated adsorbent material is treated.
[0031] Preferably, the conditions for the adsorption treatment are: temperature of 18-25℃ and time of 5-8 min.
[0032] The adsorption treatment time described in this invention refers to the residence time of the raw hydrogen peroxide in the adsorbent material. This residence time is counted from the moment the raw hydrogen peroxide begins to contact the adsorbent material until the finished hydrogen peroxide is produced. After continuous adsorption treatment, the adsorption capacity of the adsorbent material gradually increases, leading to a decrease in the total carbon concentration of the obtained finished hydrogen peroxide, which fails to meet the standard requirements. This invention preferably employs the following method for condition control to obtain a finished hydrogen peroxide that meets the requirements.
[0033] According to a preferred embodiment of the present invention, if the total carbon mass concentration c1-c2 in the finished hydrogen peroxide is less than 30 ppm, the adsorbent material that has adsorbed organic matter is subjected to extrusion regeneration and recycled; if the initial treatment capacity of the nth regenerated adsorbent material obtained after multiple extrusion regeneration processes cannot meet the requirement of c1-c2≥30 ppm, the nth regenerated adsorbent material is replaced.
[0034] According to a preferred embodiment of the present invention, if the total carbon mass concentration c1-c2 in the finished hydrogen peroxide is less than 60 ppm, the adsorbent material that has adsorbed organic matter is subjected to extrusion regeneration and recycled; if the processing capacity of the nth regenerated adsorbent material obtained after multiple extrusion regeneration processes cannot meet the requirement of c1-c2≥60 ppm, the nth regenerated adsorbent material is replaced.
[0035] Preferably, the adsorption treatment is carried out under conditions of pH 4-6.
[0036] In a preferred embodiment, the total carbon mass concentration of the raw material hydrogen peroxide is 150-500 ppm, preferably 200-500 ppm.
[0037] Preferably, the concentration of the raw material hydrogen peroxide is 27-55 wt%.
[0038] Preferably, the flow rate of the raw hydrogen peroxide through the adsorbent material is 200-1000 mL / min.
[0039] Preferably, the raw material hydrogen peroxide is derived from a device for producing propylene oxide by oxidizing propylene hydrogen peroxide.
[0040] In a preferred embodiment, the stability of the finished hydrogen peroxide is 93-98%.
[0041] The present invention preferably involves passing the raw hydrogen peroxide through a device filled with the adsorbent material for adsorption treatment to obtain the finished hydrogen peroxide. The present invention does not impose any particular limitations on the material or shape of the device, as long as it can fix the adsorbent material, ensure a continuous flow of the raw hydrogen peroxide through the adsorbent material, and prevent secondary pollution of the finished hydrogen peroxide. Further details are omitted here, and those skilled in the art should not construe this as a limitation of the present invention.
[0042] As previously stated, the second aspect of the present invention provides a finished hydrogen peroxide product prepared by the method described in the first aspect.
[0043] The decarbonization method for hydrogen peroxide provided by this invention can achieve efficient decarbonization of hydrogen peroxide and is beneficial to the subsequent production and operation of caprolactam, propylene oxide, epichlorohydrin and other equipment.
[0044] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all raw materials are commercially available products. See Table 1 for details.
[0045] Table 1
[0046]
[0047] In the following examples, the adsorbent material used is cylindrical with a diameter of 4.4 cm and a height of 40 cm, resulting in a calculated volume of 608.2 cm³. 3 When in use, the cylinder should be placed vertically.
[0048] The test method for the stability of the finished hydrogen peroxide is: W = (W2 - W1) × 100%;
[0049] Where W2 is the concentration after closed cooking (in wt%), and W1 is the concentration before cooking (in wt%).
[0050] In the following examples, the processing capacity is the same for an adsorbent material of the same volume (608.2 cm³). 3 The difference between the total carbon concentration of the treated hydrogen peroxide and that of the raw hydrogen peroxide was obtained by treating the same volume (500 mL) of raw hydrogen peroxide.
[0051] Example 1
[0052] (1) Take 500 mL of raw hydrogen peroxide and let it flow through a device filled with adsorption material. Under the conditions of pH 4-6 and temperature 20℃, the raw hydrogen peroxide stays in the adsorption material for 6 min to obtain the finished hydrogen peroxide (named S1-1).
[0053] The raw material hydrogen peroxide is raw material hydrogen peroxide I; the adsorbent material is adsorbent material I-1, and is the original adsorbent material that has not undergone extrusion and regeneration treatment;
[0054] (2) Until the aforementioned 500 mL of raw hydrogen peroxide is finished, without replacing the adsorbent material or performing extrusion regeneration on the adsorbent material, take another 500 mL of the same batch of raw hydrogen peroxide and continue to introduce it into the device filled with adsorbent material. Perform adsorption treatment under the same conditions as in step (1) to obtain the finished hydrogen peroxide (named S1-2).
[0055] (3) Step (2) is repeated 4 times to obtain finished hydrogen peroxide S1-3, finished hydrogen peroxide S1-4, finished hydrogen peroxide S1-5 and finished hydrogen peroxide S1-6 in sequence.
[0056] Example 2
[0057] (1) Take 500 mL of raw hydrogen peroxide and let it flow through a device filled with adsorption material. Under the conditions of pH 4-6 and temperature 18℃, the raw hydrogen peroxide stays in the adsorption material for 6 min to obtain the finished hydrogen peroxide (named S2-1).
[0058] The raw material hydrogen peroxide is raw material hydrogen peroxide I; the adsorbent material is adsorbent material I-2, and is the original adsorbent material that has not undergone extrusion and regeneration treatment;
[0059] (2) Until the treatment of the aforementioned 500 mL of raw hydrogen peroxide is completed, without replacing the adsorbent material or performing extrusion regeneration on the adsorbent material, take another 500 mL of the same batch of raw hydrogen peroxide and continue to introduce it into the device filled with adsorbent material. Perform adsorption treatment under the same conditions as in step (1) to obtain the finished hydrogen peroxide (named S2-2).
[0060] (3) Step (2) is repeated 4 times to obtain finished hydrogen peroxide S2-3, finished hydrogen peroxide S2-4, finished hydrogen peroxide S2-5 and finished hydrogen peroxide S2-6 in sequence.
[0061] Example 3
[0062] (1) Take 500 mL of raw hydrogen peroxide and let it flow through a device filled with adsorption material. Under the conditions of pH 4-6 and temperature 25℃, the raw hydrogen peroxide stays in the adsorption material for 6 min to obtain the finished hydrogen peroxide (named S3-1).
[0063] The raw material hydrogen peroxide is raw material hydrogen peroxide I; the adsorbent material is adsorbent material I-3, and is the original adsorbent material that has not undergone extrusion regeneration treatment;
[0064] (2) Until the treatment of the aforementioned 500 mL of raw hydrogen peroxide is completed, without replacing the adsorbent material or performing extrusion regeneration on the adsorbent material, take another 500 mL of the same batch of raw hydrogen peroxide and continue to introduce it into the device filled with adsorbent material. Perform adsorption treatment under the same conditions as in step (1) to obtain the finished hydrogen peroxide (named S3-2).
[0065] (3) Step (2) is repeated 4 times to obtain finished hydrogen peroxide S3-3, finished hydrogen peroxide S3-4, finished hydrogen peroxide S3-5 and finished hydrogen peroxide S3-6 in sequence.
[0066] The aforementioned finished hydrogen peroxide was tested, and the results are shown in Table 2:
[0067] Table 2
[0068]
[0069] Example 4
[0070] (1) In the manner of Example 1, the adsorbent material used in Example 1 is adsorbed multiple times until the adsorption amount of the adsorbent material reaches saturation (the difference between the total carbon mass concentration c1 of the raw hydrogen peroxide and the total carbon mass concentration c2 of the finished hydrogen peroxide satisfies c1-c2<30ppm). The original adsorbent material is then subjected to extrusion regeneration treatment (volume compression ratio of 5:10) to obtain a regenerated adsorbent material.
[0071] Take 500 mL of raw hydrogen peroxide II and pass it through a device filled with the aforementioned regenerated adsorption material for adsorption treatment (pH value 4-6, temperature 20℃, time 6 min) to obtain the finished hydrogen peroxide (named Z1).
[0072] (2) The raw material hydrogen peroxide II is continuously flowed through the device filled with the first regenerated adsorbent material for adsorption treatment (pH value 4-6, temperature 20℃, time 6min) until the adsorption capacity of the first regenerated adsorbent material reaches saturation (c1-c2 < 30ppm). The first regenerated adsorbent material is then subjected to extrusion regeneration treatment (volume compression ratio 5:10) to obtain the second regenerated adsorbent material.
[0073] Take 500 mL of raw hydrogen peroxide II and pass it through a device filled with the aforementioned regenerated adsorption material for adsorption treatment (pH value 4-6, temperature 20℃, time 6 min) to obtain the finished hydrogen peroxide (named Z2).
[0074] (3) The raw material hydrogen peroxide II is continuously flowed through the device filled with the 2-time regenerated adsorbent material for adsorption treatment (pH value 4-6, temperature 20℃, time 6min) until the adsorption capacity of the 2-time regenerated adsorbent material reaches saturation (c1-c2 < 30ppm). The 2-time regenerated adsorbent material is then subjected to extrusion regeneration treatment (volume compression ratio 5:10) to obtain the 3-time regenerated adsorbent material.
[0075] Take 500 mL of raw hydrogen peroxide II and pass it through a device filled with the aforementioned 3-times regenerated adsorption material for adsorption treatment (pH value 4-6, temperature 20℃, time 6 min) to obtain the finished hydrogen peroxide (named Z3).
[0076] Example 5
[0077] The process is similar to step (1) in Example 4, except that the volume compression ratio of the extrusion regeneration process is adjusted to 1:10, while the rest remains unchanged, to obtain the finished hydrogen peroxide.
[0078] Example 6
[0079] The process was carried out in a similar manner to step (1) in Example 1, except that adsorbent I-1 was replaced with an equal volume of adsorbent I-5; all other steps remained unchanged to obtain the finished hydrogen peroxide.
[0080] Example 7
[0081] The process was carried out in a similar manner to step (1) in Example 1, except that adsorbent I-1 was replaced with an equal volume of adsorbent I-6; all other steps remained unchanged to obtain the finished hydrogen peroxide.
[0082] The aforementioned finished hydrogen peroxide was tested, and the results are shown in Table 3:
[0083] Table 3
[0084]
[0085] The results above show that the technical solution claimed in this application has a high treatment efficiency for the raw material hydrogen peroxide, which not only significantly reduces production costs, but also makes regeneration simple, safe and reliable, produces little waste, and has good application prospects.
[0086] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.
Claims
1. A hydrogen peroxide decarburization technology and a method for regenerating the adsorbent material thereof, characterized in that, The method comprises: The raw material hydrogen peroxide is subjected to adsorption treatment by flowing through the adsorption material to obtain finished product hydrogen peroxide; the control condition is such that the difference between the total carbon mass concentration c1 of the raw material hydrogen peroxide and the total carbon mass concentration c2 of the finished product hydrogen peroxide satisfies c1-c2≥30 ppm; The adsorption material is selected from at least one of original adsorption material, n times regenerated adsorption material; wherein n is an integer ≥1; when n=1, the n times regenerated adsorption material is obtained by extrusion regeneration treatment of the original adsorption material; when n≥2, the n times regenerated adsorption material is obtained by extrusion regeneration treatment of (n-1) times regenerated adsorption material; The original adsorbing material is an elastic material, the original adsorbing material is selected from at least one of a polyvinyl alcohol material, a polyester material, a polyurethane material, a polyether material, and the density of the original adsorbing material is 16-60 kg / m 3 .
2. The method of claim 1, wherein, The control condition is such that the difference between the total carbon mass concentration c1 of the raw material hydrogen peroxide and the total carbon mass concentration c2 of the finished product hydrogen peroxide satisfies c1-c2≥60 ppm; and / or the density of the raw adsorbent material is 28-50 kg / m 3 .
3. The method according to claim 1 or 2, characterized in that, The volume compression ratio of the extrusion regeneration treatment is 1-5:
10.
4. The method according to any one of claims 1 to 3, characterized in that, n=1, the treatment capacity of the n times regenerated adsorption material is 80-95% of the original adsorption material.
5. The method according to any one of claims 1 to 3, characterized in that, n≥2, the treatment capacity of the n times regenerated adsorption material is 80-90% of the (n-1) times regenerated adsorption material.
6. The method according to any one of claims 1 to 5, characterized in that, The adsorption treatment condition satisfies: temperature is 18-25℃, time is 5-8 min; And / or, the adsorption treatment is carried out under the condition that the pH value is 4-6.
7. The method according to any one of claims 1 to 6, characterized in that, The total carbon mass concentration of the raw material hydrogen peroxide is 150-500 ppm; And / or, the concentration of the raw material hydrogen peroxide is 27-55 wt%.
8. The method of claim 7, wherein, The raw material hydrogen peroxide is derived from propylene hydrogen peroxide oxidation device for preparing propylene oxide.
9. The method according to any one of claims 1 to 8, characterized in that, The stability of the finished product hydrogen peroxide is 93-98%.
10. Finished product hydrogen peroxide prepared by the method of any one of claims 1-9.