CN1246286C - Method for recovering p-hydroxybenzoic acid from water drain of production of p-hydroxybenzoic acid - Google Patents
Method for recovering p-hydroxybenzoic acid from water drain of production of p-hydroxybenzoic acid Download PDFInfo
- Publication number
- CN1246286C CN1246286C CN200410041229.6A CN200410041229A CN1246286C CN 1246286 C CN1246286 C CN 1246286C CN 200410041229 A CN200410041229 A CN 200410041229A CN 1246286 C CN1246286 C CN 1246286C
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- CN
- China
- Prior art keywords
- hydroxybenzoic acid
- resin
- phenol
- water
- nda
- Prior art date
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- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 39
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003795 desorption Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003463 adsorbent Substances 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000010842 industrial wastewater Substances 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000003480 eluent Substances 0.000 abstract 1
- 238000010828 elution Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195357 gramphenol Natural products 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 208000006558 Dental Calculus Diseases 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention discloses a method for recovering p-hydroxybenzoic acid from discharged water of p-hydroxybenzoic acid preparation. Industrial wastewater (the p-hydroxybenzoic acid contained in the industrial wastewater is about 2700 mg/L, and phenol is about 1300 mg/L.) containing p-hydroxybenzoic acid, which is discharged in the preparation process, passes through NDA-101, etc. macroporous absorption resin bed layers, the p-hydroxybenzoic acid and the phenol are absorbed on resin, and thereby, the p-hydroxybenzoic acid is effectively separated from a water phase. After the absorption operation of the resin, diluted alkali liquid is used for elution, the obtained eluent containing p-hydroxybenzoic acid and a small amount of phenol can be directly returned to the acidolysis step of the preparation process for recovery. After being eluted, the resin can be recycled.
Description
Technical field
The present invention relates to P-hydroxybenzoic acid, specifically, relate to from P-hydroxybenzoic acid production draining and reclaim P-hydroxybenzoic acid.
Background technology
P-hydroxybenzoic acid is a kind of broad-spectrum organic synthesis raw material, and its esters product can be cooked foodstuff additive, is used to produce soy sauce, vinegar, refreshment drink, fruit seasonings etc., also is widely used in aspects such as producing makeup, medicine, sanitas and sterilant.The synthetic route of present domestic main employing solvent carboxylation method; In the draining of workshop section is filtered in acid adjustment, contain about 2700mg/L of P-hydroxybenzoic acid and the about 1300mg/L of phenol, also contain have an appointment 1% sulfuric acid and vitriolate of tartar and a spot of Whitfield's ointment in addition.
Summary of the invention
The purpose of this invention is to provide a kind of technical scheme, effectively product P-hydroxybenzoic acid and the raw material phenol that runs off in the enriching and recovering draining.
Technical scheme of the present invention is as follows:
Reclaim the method for P-hydroxybenzoic acid in a kind of P-hydroxybenzoic acid production draining, it is made up of the following step:
1. with P-hydroxybenzoic acid production draining after filtering, be under the condition of 0.5～3BV/h (BV is the resin bed volume) by being filled with the adsorption tower of macroporous adsorbent resin with filtrate at 0～35 ℃ and flow, organism such as P-hydroxybenzoic acid in the water are attracted on the resin, the absorption effluent water white transparency.
With concentration be the NaOH solution of 1～3mol/L and water as desorbing agent, will adsorb the macroporous adsorbent resin desorption and regeneration of P-hydroxybenzoic acid and phenol, desorption temperature is 60～80 ℃, the flow of desorbing agent is 0.5～2BV/h.
3. the high density elutriant that preceding 2/5 volume elutes returns the acid out operation in the P-hydroxybenzoic acid production process, and back 3/5 volume lower concentration elutriant is used to prepare next batch desorbing agent recycled.
Above-mentioned macroporous adsorbent resin can be the macroporous adsorbent resin that home-made NDA-101 resin, NDA-88 resin, CHA-101 resin, H-103 resin or JX resin etc. have high-specific surface area, preferably polymeric adsorbent NDA-101.
The present invention can adopt double-column in series absorption, and the operation scheme of single tower desorption promptly is provided with I, II, three adsorption towers of III, with I, II tower series connection following current absorption, the I tower is as first post earlier, and the II tower is as stern post, after the absorption of I tower is saturated, switch to II, III tower series connection following current absorption, the II tower is as first post, and the III tower is as stern post, the I tower carries out the following current desorption simultaneously, so cyclical operation can guarantee the operation continuously all the time of whole device, can improve the service efficiency of resin simultaneously.
The present invention can make the incarnadine strongly-acid production draining that includes about 2700mg/L P-hydroxybenzoic acid and about 1300mg/L phenol after the above-mentioned processing of process, the water outlet water white transparency, and organic content is less than 5mg/L.Water outlet can be according to wherein comprehensive utilization or the directly discharging of neutralization back that production workshop section makes washing water or carries out spent acid returned in the difference of acid content and the requirement of producer.Can from draining per ton, reclaim about 2 kilograms of P-hydroxybenzoic acid, about 1 kilogram of phenol according to this inventive method.
Embodiment
Below further specify the present invention by example.
Embodiment 1: 100ml (about 70 gram) NDA-101 macroporous adsorbent resin (productions of dagger-axe moral environmental protection Science and Technology Co., Ltd. of Jiangsu Nanjing University) is packed in the glass adsorption column that strap clamp overlaps, and (Φ 32 * 360mm).Under 0～5 ℃, the process water that discharges in the P-hydroxybenzoic acid production process is filtered, filtrate is passed through resin bed with the flow of 300ml/h, treatment capacity is that 800ml/ criticizes, the concentration of former water P-hydroxybenzoic acid is about 2650mg/L, phenol concentration is about 1210mg/L, the absorption effluent water white transparency, and wherein the total concn of P-hydroxybenzoic acid and phenol is about 0.5mg/L.
Use the NaOH aqueous solution and the flow following current with 200ml/h under 75 ± 5 ℃ temperature of 300ml distilled water of 200ml 3mol/L to carry out desorption by resin bed, the desorption rate of P-hydroxybenzoic acid＞98% successively.Just begin effusive 200ml desorption liquid and be yellow, be high concentration desorption liquid, interior 1.6 gram P-hydroxybenzoic acid and the 0.8 gram phenol of containing approximately, it is returned to the acid out operation in the P-hydroxybenzoic acid production process.Effusive afterwards is light concentration desorption liquid, as preparation next batch desorbing agent.
Embodiment 2: 100ml (about 70 gram) NDA-101 macroporous adsorbent resin (productions of dagger-axe moral environmental protection Science and Technology Co., Ltd. of Jiangsu Nanjing University) is packed in the glass adsorption column that strap clamp overlaps, and (Φ 32 * 360mm).Under 30～35 ℃, the process water that discharges in the P-hydroxybenzoic acid production process is filtered, filtrate is passed through resin bed with the flow of 50ml/h, treatment capacity is that 800ml/ criticizes, the concentration of former water P-hydroxybenzoic acid is about 2650mg/L, phenol concentration is about 1210mg/L, the absorption effluent water white transparency, and wherein the total concn of P-hydroxybenzoic acid and phenol is about 0.5mg/L.
Use the NaOH aqueous solution and the flow following current with 50ml/h under 65 ± 5 ℃ temperature of 450ml distilled water of 300ml1mol/L to carry out desorption by resin bed, the desorption rate of P-hydroxybenzoic acid＞98% successively.Just begin effusive 300ml desorption liquid and be yellow, be high concentration desorption liquid, interior 1.6 gram P-hydroxybenzoic acid and the 0.8 gram phenol of containing approximately, it is returned to the acid out operation in the P-hydroxybenzoic acid production process.Effusive afterwards is light concentration desorption liquid, as preparation next batch desorbing agent.
Embodiment 3: (Φ 600 * 3500mm) to select three identical 316L stainless steel adsorption towers of specification for use, every tower filling 600 kilograms of resins of NDA-101 (about 800L), (15～20 ℃) are with the draining in the P-hydroxybenzoic acid production process (the about 12820mg/L of CODcr) under the room temperature, squeeze into adsorption tower after filtering, the method of I, II tower double-column in series following current absorption is adopted in absorption, and absorption flow is controlled at 1.6m
3/ h, every batch processing amount is controlled at 8m
3Waste water after treatment, the outlet water organic substance total concn is reduced to 5mg/L.Water outlet can fully utilize or discharge with in the diluted alkaline and back.
Adsorbing 8m
3The first post I adsorption tower of waste water NaOH aqueous solution desorption.Earlier raffinate in No. 1 tower is drained, and, make it be preheated to 75 ℃, use 1.6m successively with hot water adverse current injection I adsorption tower
32mol/LNaOH solution and 2.4m
3Tap water with 0.8m
3The flow of/h carries out the following current desorption, preceding 1.6m
3Desorption liquid return acid out operation in the P-hydroxybenzoic acid production process, back 2.4m
3Desorption liquid put into storage tank, be used to prepare the next batch desorbing agent.
Embodiment 4: the macroporous adsorbent resin among the embodiment 1 is used instead be NDA-88 resin (dagger-axe moral environmental protection Science and Technology Co., Ltd. of Jiangsu Nanjing University) or CHA-101 resin, CHA-111 resin (production of development chemical plant, changzhou city), JX-101 resin (production of Golden Elephant chemical plant, Danyang City, Jiangsu), H-103 resin (Chemical Plant of Nankai Univ.'s production), except that adsorption treatment amount and adsorption effect slightly the difference, its result is substantially the same manner as Example 1.
Claims (3)
1. reclaim the method for P-hydroxybenzoic acid in the P-hydroxybenzoic acid production draining, it is characterized in that it is made up of the following step:
One. with P-hydroxybenzoic acid production draining after filtering, with filtrate be at 0～35 ℃ and flow under the condition of 0.5～3BV/h by being filled with the adsorption tower of macroporous adsorbent resin, P-hydroxybenzoic acid and phenol in the water are attracted on the resin,
Two, with concentration be the NaOH solution of 1～3mol/L and water as desorbing agent, will adsorb the macroporous adsorbent resin desorption and regeneration of P-hydroxybenzoic acid and phenol, desorption temperature is 60～80 ℃, the flow of desorbing agent is 0.5～2BV/h,
Three, the high density elutriant that elutes of preceding 2/5 volume returns the acid out operation in the P-hydroxybenzoic acid production process, and back 3/5 volume lower concentration elutriant is used to prepare next batch desorbing agent recycled.
2. method according to claim 1 is characterized in that: above-mentioned macroporous adsorbent resin is NDA-101, NDA-88 resin, CHA-101 resin, H-103 resin or JX resin.
3. method according to claim 2 is characterized in that: macroporous adsorbent resin is the NDA-101 resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410041229.6A CN1246286C (en) | 2004-06-10 | 2004-06-10 | Method for recovering p-hydroxybenzoic acid from water drain of production of p-hydroxybenzoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410041229.6A CN1246286C (en) | 2004-06-10 | 2004-06-10 | Method for recovering p-hydroxybenzoic acid from water drain of production of p-hydroxybenzoic acid |
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| Publication Number | Publication Date |
|---|---|
| CN1583705A CN1583705A (en) | 2005-02-23 |
| CN1246286C true CN1246286C (en) | 2006-03-22 |
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| CN200410041229.6A Expired - Fee Related CN1246286C (en) | 2004-06-10 | 2004-06-10 | Method for recovering p-hydroxybenzoic acid from water drain of production of p-hydroxybenzoic acid |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319019B (en) * | 2013-06-14 | 2016-06-01 | 陕西蓝深特种树脂有限公司 | A kind of aspartame produces disposing mother liquor treatment process and system |
| CN103395925A (en) * | 2013-07-30 | 2013-11-20 | 苏州思睿屹新材料股份有限公司 | Treatment method for recycling para-hydroxybenzoic acid wastewater |
| CN104003867B (en) * | 2014-05-22 | 2015-08-05 | 江苏宝众宝达药业有限公司 | Method for recovering p-hydroxyphenylacetic acid from waste liquid |
| CN111303002B (en) * | 2020-02-28 | 2021-05-07 | 浙江工业大学 | Method for treating fosinopril intermediate mother liquor |
| CN112275329B (en) * | 2020-09-30 | 2022-08-05 | 石家庄惠洁科技有限公司 | Clean production process of 122 type cation exchange resin |
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- 2004-06-10 CN CN200410041229.6A patent/CN1246286C/en not_active Expired - Fee Related
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| CN1583705A (en) | 2005-02-23 |
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