CN1386736A - Process for preparing nicotinic acid - Google Patents
Process for preparing nicotinic acid Download PDFInfo
- Publication number
- CN1386736A CN1386736A CN02112099A CN02112099A CN1386736A CN 1386736 A CN1386736 A CN 1386736A CN 02112099 A CN02112099 A CN 02112099A CN 02112099 A CN02112099 A CN 02112099A CN 1386736 A CN1386736 A CN 1386736A
- Authority
- CN
- China
- Prior art keywords
- acid
- nicotinic acid
- production method
- nitric acid
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229960003512 nicotinic acid Drugs 0.000 title claims abstract description 35
- 235000001968 nicotinic acid Nutrition 0.000 title claims abstract description 35
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 238000007664 blowing Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000033116 oxidation-reduction process Effects 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 claims description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 239000006096 absorbing agent Substances 0.000 abstract 1
- 238000000066 reactive distillation Methods 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- -1 Nicotinic acid Nitric acid Sulfuric acid Chemical compound 0.000 description 1
- MXOSECBTSFQUJS-UHFFFAOYSA-N [O-2].[Ti+4].[V+5] Chemical compound [O-2].[Ti+4].[V+5] MXOSECBTSFQUJS-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- XQOKRXQBCUEKAE-UHFFFAOYSA-N potassium;pyridine-3-carboxylic acid Chemical compound [K].OC(=O)C1=CC=CN=C1 XQOKRXQBCUEKAE-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Pyridine Compounds (AREA)
Abstract
A process for industrial preparing nicotinic acid from beta-methyl pyridine as raw material and the mixture of nitric acid and sulfuric acid as oxidant is characterized by that under negative or low pressure, a reactive distillation method is used to maintain the temp of oxidizing reaction at desired value, the oxidizing reactor is communicated with low-temp absorber for absorbing NOx generated in reaction by diluted nitric acid to obtain high-concentration (greater than 40%) nitric acid for reusing it in oxidizing reaction, and the rest of NOx is introduced into oxidizing-reducing furnace to obtain CO2 and N2. Its advantages are high conversion (more than 98%), and no environmental pollution.
Description
Technical field
The present invention relates to the production method of nicotinic acid.Nicotinic acid, formal name used at school pyridine-β-formic acid is applied to fields such as medicine, food, feed, also can make plant-growth regulator, the intermediate of sterilant.
Background technology
Up to now be that the method that raw material is produced nicotinic acid has with the beta-picoline:
1) KMnO
4Oxidation style.It is with beta-picoline KMnO
4Be oxidized to nicotinic acid potassium, acidifying becomes nicotinic acid again.This method KMnO
4Consumption is big, and general quantity is potassium permanganate/beta-picoline＞2 (mol ratios); Because cost height, waste residue are handled and are difficult for, and can only be used for prepared in laboratory.2) Oxygen Catalytic Oxidation method.Chinese patent CN1247190, it is catalyzer that CN139922 proposes with vanadium-titanium oxide, in the presence of steam, comes the oxidation beta-picoline with oxygen, the advantage of this method is not for generating deleterious tail gas and waste liquid.Shortcoming is that the oxygen consumption is big, and the steam consumption is also very big, and reactor volume efficient is low, and energy consumption is very high, deleterious catalyst waste slag difficult treatment.3) in the presence of catalyzer such as vanadium, beta-picoline is the beta-cyano pyridine by ammonia and air mixture ammonia oxidation, is hydrolyzed to nicotinic acid again.Advantage is that raw materials cost is low; Shortcoming is to produce to have certain danger, and catalyst waste slag is difficult for handling, and waste sludge discharge has poisonous cyano group thing.4) nitric acid oxidation method.Chinese patent CN1141288 proposes to use the nitric acid oxidation beta-picoline, produces nicotinic acid.Wherein, embodiment feeds nitric acid (68～70%) gradually in beta-picoline vitriol under normal pressure, 195 ± 5 ℃, absorbs tail gas NO with alkali lye
xBecause reaction has produced azeotrope, so can't keep required temperature of reaction, causes the oxidation ratio very low (per pass conversion is low) of beta-picoline; Secondly, well-known, with alkali absorption of N O
x, specific absorption is very low, and generally only 10～20%, most NO
xCan't absorb, be discharged, and the nitrate quantity discharged is also very big, this method can't realize suitability for industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of product yield height, the method that is suitable for suitability for industrialized production nicotinic acid free from environmental pollution.
The production method of nicotinic acid of the present invention is to adopt the reaction distillation method that beta-picoline vitriol is melted into the liquid stills for air blowing that add, with nitric acid-sulfuric acid mixing acid is the speed adding stills for air blowing of oxygenant by 10～150L/h, consumption (by weight) is an oxygenant: beta-picoline vitriol is 3～7: 1,140～220 ℃ of temperature, carry out oxidizing reaction under-0.06～0.06Mpa pressure, stills for air blowing link to each other with the low temperature absorption device, the NOx that reaction is discharged introduces the low temperature absorption device, absorb with rare nitric acid, a small amount of unabsorbed NOx introduces the oxidation-reduction stove, through scorching hot carbon-coating, generate CO
2, N
2Discharging again, it is 3～4 that the nicotinic acid-N-vitriol of reaction gained is neutralized to the pH value with NaOH, removes Na with Steppecd crystallization
2SO
4Get crude product nicotinic acid,, add decolorizing with activated carbon, filter the back recrystallization and make elaboration nicotinic acid again with crude product nicotinic acid water dissolution.
The content of each composition of mixing acid (by weight) is among the present invention:
Nitric acid 30～70% sulfuric acid 5～15% water 20～60%
Optimum content (by weight) is:
Nitric acid 40～60% sulfuric acid 6～10% water 30～50%
Among the present invention, the speed of oxygenant adding stills for air blowing is 80～110L/h preferably.
The temperature of oxidizing reaction is preferably 160～190 ℃.
The temperature of low temperature absorption device is-5～10 ℃.Be preferably-2～-5 ℃.
The rare concentration of nitric acid that absorbs usefulness is 10～15%.
The temperature of oxidation-reduction stove is 400～1000 ℃.With 600～800 ℃ is good.
The present invention has the following advantages:
1) the present invention is an oxygenant with nitric acid-vitriolic mixing acid, under negative pressure or low pressure, adopts the reaction distillation method to make oxidizing reaction maintain required temperature, and the per pass conversion of beta-picoline＞98% can realize making with high yield nicotinic acid.
2) because the present invention adopts the low temperature absorption method, with rare nitric acid absorption of N O
x, can generate the nitric acid of concentration＞40%, be reused for oxidizing reaction, NO
xSpecific absorption＞90%.This method greatly reduces the actual consumption of nitric acid, does not have the nitrate discharging.
3) the present invention is to unabsorbed NO
x, make it pass through the oxidation-reduction stove, through scorching hot carbon-coating, generate CO
2, N
2Discharging does not cause environmental pollution again.
Embodiment
Embodiment 1
In stills for air blowing, add beta-picoline vitriol 400Kg, stir and be warming up to 170 ℃, the 900L oxygenant is added stills for air blowing with the speed of 100L/h from elevated dosing vessel.
Oxygenant consists of: nitric acid 60%, and sulfuric acid 5%, water 35% is in-negative pressure of 0.02Mpa stills for air blowing, and in the control still 170～180 ℃, oxidizing reaction 2 hours.
NO is discharged in oxidation
xAbsorb with 10% rare nitric acid, 0～2 ℃ of absorption temperature is total to such an extent that reclaim nitric acid 1100L, and concentration is 41%.
Unabsorbed NO
xFeed the oxidation-reduction stove, by 600 ℃ carbon-coating, NO
xAll become CO
2With N
2Discharging.
Oxidation products is nicotinic acid-N-vitriol, and in sending into and still, being neutralized to the pH value with 30%NaOH solution is 3～4, obtain nicotinic acid and sodium sulfate, use Steppecd crystallization, remove sodium sulfate, obtain nicotinic acid crude product 255Kg, content is 87.5%, with recrystallization behind the decolorizing with activated carbon, get nicotinic acid elaboration 211Kg, yield is 102% (weight), content is 99.5%, 236.5～237.2 ℃ of fusing points.
Embodiment 2
The oxygenant add-on is 800L, and all the other are identical with example 1, obtains elaboration nicotinic acid 188Kg, and yield is 94% (weight), content 99.3%, and 237.2～237.5 ℃ of fusing points reclaim nitric acid 900L, concentration 39%.
Embodiment 3
Comparative example (nitric acid oxidation method), oxygenant are nitric acid 70%, water 30%, atmospheric pressure oxidation, do not distill, be warming up to 195 ℃, with the speed adding oxygenant 900L of 100L/h, all the other are handled with example 1, get elaboration nicotinic acid 147Kg, yield is 73.5% (weight), content 94.5%, 234～235 ℃ of fusing points.(the little Huang of product color is because due to the oxidizing temperature height.)
Embodiment 4
Comparative example (nitric acid oxidation method), all the other are identical with example 1, tail gas NO
xUse 30%NaOH, three grades of series connection absorb, and in the discharging tail gas a large amount of NO are arranged
x, form a Huanglong, reclaiming nitric acid is zero.
Embodiment 5
Comparative example (nitric acid oxidation method), oxygenant are nitric acid 30%, and water 70% adds oxygenant 1800L with 100L/h speed, all the other are handled with example 1, get elaboration nicotinic acid 88Kg, product yield 44% (weight), content 99%, 234～237 ℃ of fusing points reclaim nitric acid 2000L, concentration 25.5%.
Table 1 further provides example of the present invention, and is obvious from example, adopts the present invention to produce nicotinic acid yield height.Every batch in table 1 is thrown beta-picoline vitriol: 400Kg
| ??No | Oxygenant is formed (%) | Oxidant content (L) | Temperature of reaction ℃ | Reaction pressure MPa | Nicotinic acid | |||
| Nitric acid | Sulfuric acid | Water | Product (Kg) | Fusing point (℃) | ||||
| ??1 | ???60 | ???5 | ???35 | ??????900 | ?170～180 | ??-0.05 | ???211 | ??236.5～237.2 |
| ??2 | ???60 | ???5 | ???35 | ??????800 | ?170～180 | ??-0.05 | ???188 | ??237.2～237.5 |
| ??3 | ???30 | ???10 | ???60 | ??????2000 | ?170～175 | ??0.05 | ???192 | ??236.1～237.2 |
| ??4 | ???40 | ???5 | ???55 | ??????1500 | ?165～175 | ??0.02 | ???209 | ??235～237 |
| ??5 | ???40 | ???5 | ???55 | ??????1500 | ?165～175 | ??0.5 | ???220 | ??235～237 |
| ??6 | ???45 | ???5 | ???50 | ??????1500 | ?170～175 | ??0.6 | ???221 | ??236～237 |
| ??7 | ???45 | ???5 | ???50 | ??????1400 | ?170～175 | ??0.5 | ???225 | ??236～237 |
| ??8 | ???50 | ???5 | ???45 | ??????1300 | ?165～175 | ??0.5 | ???215 | ??236.1～237.5 |
| ??9 | ???50 | ???5 | ???45 | ??????1300 | ?165～175 | ??0.6 | ???221 | ??235～237 |
Claims (10)
1. the production method of nicotinic acid, it is characterized in that adopting the reaction distillation method that beta-picoline vitriol is melted into the liquid stills for air blowing that add, with nitric acid-sulfuric acid mixing acid is the speed adding stills for air blowing of oxygenant by 10～150L/h, consumption (by weight) is an oxygenant: beta-picoline vitriol is 3～7: 1,140～220 ℃ of temperature, carry out oxidizing reaction under-0.06～0.06Mpa pressure, stills for air blowing link to each other with the low temperature absorption device, the NOx that reaction is discharged introduces the low temperature absorption device, absorb with rare nitric acid, a small amount of unabsorbed NOx introduces the oxidation-reduction stove, through scorching hot carbon-coating, generates CO
2, N
2Discharging again, it is 3～4 that the nicotinic acid-N-vitriol of reaction gained is neutralized to the pH value with NaOH, removes Na with Steppecd crystallization
2SO
4Get crude product nicotinic acid,, add decolorizing with activated carbon, filter the back recrystallization and make elaboration nicotinic acid again with crude product nicotinic acid water dissolution.
2. by the production method of the described nicotinic acid of claim 1, it is characterized in that the content (weight) of each composition of mixing acid is:
Nitric acid 30～70% sulfuric acid 5～15% water 20～60%
3. by the production method of the described nicotinic acid of claim 1, it is characterized in that the content (by heavy) of each composition of mixing acid is:
Nitric acid 40～60% sulfuric acid 6～10% water 30～50%
4. by the production method of the described nicotinic acid of claim 1, it is characterized in that the speed of oxygenant adding stills for air blowing is 80～110L/h.
5. by the production method of the described nicotinic acid of claim 1, the temperature that it is characterized in that oxidizing reaction is 160～190 ℃.
6. by the production method of the described nicotinic acid of claim 1, it is characterized in that the temperature of low temperature absorption device is-5～10 ℃.
7. by the production method of the described nicotinic acid of claim 1, the temperature that it is characterized in that the low temperature absorption device is-2～-5 ℃.
8. by the production method of the described nicotinic acid of claim 1, the rare concentration of nitric acid that it is characterized in that absorbing usefulness is 10～15%.
9. by the production method of the described nicotinic acid of claim 1, the temperature that it is characterized in that the oxidation-reduction stove is 400～1000 ℃.
10. by the production method of the described nicotinic acid of claim 1, the temperature that it is characterized in that the oxidation-reduction stove is 600～800 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021120994A CN1219767C (en) | 2002-06-13 | 2002-06-13 | Process for preparing nicotinic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021120994A CN1219767C (en) | 2002-06-13 | 2002-06-13 | Process for preparing nicotinic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1386736A true CN1386736A (en) | 2002-12-25 |
| CN1219767C CN1219767C (en) | 2005-09-21 |
Family
ID=4741894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021120994A Expired - Fee Related CN1219767C (en) | 2002-06-13 | 2002-06-13 | Process for preparing nicotinic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1219767C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812058A (en) * | 2021-01-19 | 2021-05-18 | 绵阳市崴尼达医药科技有限责任公司 | Method for recovering organic matters in nicotinic acid production wastewater |
-
2002
- 2002-06-13 CN CNB021120994A patent/CN1219767C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812058A (en) * | 2021-01-19 | 2021-05-18 | 绵阳市崴尼达医药科技有限责任公司 | Method for recovering organic matters in nicotinic acid production wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1219767C (en) | 2005-09-21 |
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