WO2022007288A1 - 一种dl-对羟基苯海因及其硫酸脲/硫酸铵生产工艺 - Google Patents

一种dl-对羟基苯海因及其硫酸脲/硫酸铵生产工艺 Download PDF

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WO2022007288A1
WO2022007288A1 PCT/CN2020/128662 CN2020128662W WO2022007288A1 WO 2022007288 A1 WO2022007288 A1 WO 2022007288A1 CN 2020128662 W CN2020128662 W CN 2020128662W WO 2022007288 A1 WO2022007288 A1 WO 2022007288A1
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concentration
urea
ammonium sulfate
temperature
sulfate
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PCT/CN2020/128662
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English (en)
French (fr)
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卢余伟
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定陶三化药业有限公司
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Priority to ES202090071A priority Critical patent/ES2895202R1/es
Publication of WO2022007288A1 publication Critical patent/WO2022007288A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C9/00—Fertilisers containing urea or urea compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/02—Salts; Complexes; Addition compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
    • C07D233/78—Radicals substituted by oxygen atoms
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals

Definitions

  • the invention relates to the technical field of DL-p-hydroxytrihydantoin, in particular to a production process of DL-p-hydroxytrihydantoin and urea sulfate/ammonium sulfate thereof.
  • the domestic DL-p-hydroxybenzene hydantoin production technology all adopts the hydrochloric acid method synthesis process route, and this production technology has the following defects: 1.
  • a large amount of harmful HCL gas is generated, which has an impact on the production environment and production equipment, and requires Purification treatment with adsorption tower: 2.
  • a large amount of solid hazardous waste is generated in the process of wastewater treatment, which needs to be treated by a special hazardous waste treatment company. The content is high.
  • the biggest disadvantage of using the hydrochloric acid synthesis process route is the large amount of solid waste generated, the difficulty of wastewater treatment and the high cost, especially the large amount of solid waste generated in the production process has become the biggest obstacle affecting the normal production of enterprises.
  • the object of the present invention is to overcome the technological defect of producing DL-p-hydroxybenzohydantoin by the hydrochloric acid method, and to solve the difficult problems of three wastes treatment, large amount of solid waste and high cost in the above-mentioned production process.
  • glyoxylic acid, phenol, urea and sulfuric acid are used as raw materials, and the DL-p-hydroxybenzohydantoin product is obtained by condensation, suction filtration, centrifugal washing and drying according to a certain molar ratio.
  • the production mother liquor is concentrated and decomposed at high temperature, and the organic products are removed by pressure distillation, and then a certain amount of ammonia is added for neutralization. After reaction, cooling, crystallization, and separation, urea sulfate/ammonium sulfate products that meet the domestic compound fertilizer production and use are produced.
  • the invention provides the following technical solutions: a kind of DL-p-hydroxytrihydantoin and its urea sulfate/ammonium sulfate production process, comprising the following steps:
  • Step 1 add phenol, urea, and sulfuric acid to the reaction kettle according to the molar ratio, slowly heat up, control the reaction temperature at 70-95 ° C, and keep the temperature for 30 min;
  • Step 2 Add glyoxylic acid dropwise to the reaction solution of Step 1, and the dropwise addition time is controlled within 2-8h;
  • Step 3 After the dropwise addition reaction is completed, control the temperature in the reaction kettle to not be lower than 85°C, and discharge the material after keeping the temperature for 2-5h;
  • Step 4 Put the material in the reaction kettle into the prepared filter, filter with suction until there are no visible water droplets on the surface of the material, and then move the material to the prepared centrifuge while it is still hot;
  • Step 5 Put the prepared hot water not lower than 85°C into the centrifuge, overflow the surface of the material, and after centrifugal washing 3 times, pack the material and send it to drying, and then dry until the water content is not higher than 0.5 %, packaged finished product;
  • Step 6 the filtration mother liquor and washing water are combined and collected, and part is transferred to step 1 for use, and the remaining part is transferred to mother night and concentrated to recover urea sulfate/ammonium sulfate product;
  • Step 7 adding the recovered mother liquor into the concentration kettle, controlling the temperature in the concentration kettle to be no higher than 115°C, controlling the distillation time according to the actual situation, and then collecting the distillate;
  • Step 8 in the regulating tank, add ammonia water to the mother liquor to adjust the pH value range to 1-5.5, then add it to the concentration kettle for concentration, after the concentration, the concentrated solution is pumped into the ammonium sulfate crystallization kettle at high temperature for cooling and crystallization, and the crude product ammonium sulfate is obtained by centrifugal separation. ; The separation liquid is returned to the concentration system to concentrate;
  • Step 9 put the cooling liquid in the concentration kettle into the cooling liquid centrifuge in the crystallization kettle for separation, separate out the by-product urea sulfate/ammonium sulfate product, and return the separated liquid to the concentration kettle to continue to concentrate;
  • Step 10 When the concentration kettle is heated to 100°C, a large amount of water is distilled out, and part of it is separated into condensed water by the tower, which is sent to the wastewater treatment system for treatment, and part of the water vapor is discharged.
  • the molar ratio of phenol:urea:sulfuric acid is (0.5-1.0):(0.9-1.3):(0.9-1.3).
  • the catalyst in the step 1 is sulfuric acid with a concentration of 36-75%.
  • the amount of glyoxylic acid with a concentration of 40-75% added dropwise is 1.0-1.4 moles.
  • ammonia water is added to the concentrated solution for neutralization.
  • the temperature in the concentration kettle is not higher than 115°C, and is cooled to normal temperature after the reaction.
  • the separated liquid is returned to the concentration kettle to continue the concentration treatment, and is discharged after passing the treatment.
  • the content of urea sulfate is 8-12%, and the content of ammonium sulfate is 85-95%.
  • the beneficial effects of the present invention are as follows: compared with the synthesis of DL-parahydroxybenzohydantoin products by the hydrochloric acid method, the product quality and yield of the present invention are improved, and the synthesis of DL-parahydroxyl by the hydrochloric acid method is solved.
  • the product quality and yield of the present invention are improved, and the synthesis of DL-parahydroxyl by the hydrochloric acid method is solved.
  • a large amount of HCL gas is released on the production site, and the impact of other organic substances such as waste hydrochloric acid on the production environment and production equipment is effectively solved.
  • the urea sulfate/ammonium sulfate by-products recovered by the present invention can be directly used for compound fertilizer production, which not only reduces the cost of wastewater treatment , and increase the economic benefits; the waste water generated in the production process can be discharged up to the standard after micro-electrolysis, filtration resin absorption, flocculation and decolorization, and reverse osmosis membrane filtration.
  • Fig. 1 is the production process flow chart of synthesizing DL-p-hydroxybenzohydantoin by sulfuric acid method of the present invention
  • Fig. 2 is DL-p-hydroxybenzohydantoin main reaction chemical formula of the present invention
  • Fig. 3 is the chemical formula of the side reaction of DL-p-hydroxydihydantoin of the present invention.
  • a kind of DL-p-hydroxy trihydantoin and its urea sulfate/ammonium sulfate production process comprises the following steps:
  • Step 1 add phenol, urea, and sulfuric acid to the reaction kettle according to the molar ratio, slowly heat up, control the reaction temperature at 70-95 ° C, and keep the temperature for 30 min;
  • Step 2 Add glyoxylic acid dropwise to the reaction solution of Step 1, and the dropwise addition time is controlled within 2-8h;
  • Step 3 After the dropwise addition reaction is completed, control the temperature in the reaction kettle to not be lower than 85°C, and discharge the material after keeping the temperature for 2-5h;
  • Step 4 Put the material in the reaction kettle into the prepared filter, filter with suction until there are no visible water droplets on the surface of the material, and then move the material to the prepared centrifuge while it is still hot;
  • Step 5 Put the prepared hot water not lower than 85°C into the centrifuge, overflow the surface of the material, and after centrifugal washing 3 times, pack the material and send it to drying, and then dry until the water content is not higher than 0.5 %, packaged finished product;
  • Step 6 the filtration mother liquor and washing water are combined and collected, and part is transferred to step 1 for use, and the remaining part is transferred to mother night and concentrated to recover urea sulfate/ammonium sulfate product;
  • Step 7 adding the recovered mother liquor into the concentration kettle, controlling the temperature in the concentration kettle to be no higher than 115°C, controlling the distillation time according to the actual situation, and then collecting the distillate;
  • Step 8 in the regulating tank, add ammonia water to the mother liquor to adjust the pH value range to 1-5.5, then add it to the concentration kettle for concentration, after the concentration, the concentrated solution is pumped into the ammonium sulfate crystallization kettle at high temperature for cooling and crystallization, and the crude product ammonium sulfate is obtained by centrifugal separation. ; The separation liquid is returned to the concentration system to concentrate;
  • Step 9 put the cooling liquid in the concentration kettle into the cooling liquid centrifuge in the crystallization kettle for separation, separate out the by-product urea sulfate/ammonium sulfate product, and return the separated liquid to the concentration kettle to continue to concentrate;
  • Step 10 When the concentration kettle is heated to 100°C, a large amount of water is distilled out, and part of it is separated into condensed water by the tower, which is sent to the wastewater treatment system for treatment, and part of the water vapor is discharged.
  • the mol ratio of phenol: urea: sulfuric acid is (0.5-1.0): (0.9-1.3): (0.9-1.3).
  • the catalyst in the step 1 is sulfuric acid with a concentration of 36-75%.
  • the amount of glyoxylic acid with a concentration of 40-75% added dropwise is 1.0-1.4 moles.
  • the temperature in the concentration kettle is not higher than 115 ° C, and the reaction is cooled to normal temperature
  • the separated liquid is returned to the concentration kettle to continue the concentration treatment, and is discharged after passing the treatment.
  • the content of urea sulfate is 8-12%, and the content of ammonium sulfate is 85-95%.
  • Step 1 in the 2000L enamel reaction kettle, 500L of the reaction mother liquor, start stirring, then add 250Kg of urea, 170Kg of phenol, and 180L of sulfuric acid with a concentration of 60% to the reaction kettle, slowly control the reaction temperature at 90 ° C, and keep the temperature for 30min;
  • Step 2 After the heat preservation is completed, add 255Kg of weighed 50% glyoxylic acid dropwise to the reaction kettle, control the reaction temperature in the kettle not to exceed 90°C, and the dropwise addition time to not be less than 4h;
  • Step 3 After the dropwise addition reaction is completed, control the reaction temperature to not be lower than 85°C and keep the temperature for 30min; then cool down to 85°C and prepare to discharge;
  • Step 4 Put the material in the reaction kettle into the prepared filter, filter with suction until there are no visible water droplets on the surface of the material, and then move the material to the prepared centrifuge while it is still hot;
  • Step 5 Put the prepared hot water not lower than 85°C into the centrifuge, overflow the surface of the material, and after centrifugal washing 3 times, pack the material and send it to drying, and then dry until the water content is not higher than 0.5 %, packaged finished product;
  • Step 6 the filtration mother liquor and the washing water are combined and collected, a part is transferred to step 1 for use, and the remaining part is transferred to the mother liquor for concentration, and the urea sulfate/ammonium sulfate product is recovered;
  • Step 7 adding the recovered mother liquor into the concentration kettle, controlling the temperature in the concentration kettle to not be lower than 115 °C, distilling for 4 hours, and collecting the distillate;
  • Step 8 in the regulating tank, add ammonia water to the mother liquor to adjust the pH value range to 1-5.5, then add it to the concentration kettle for concentration, after the concentration, the concentrated solution is pumped into the ammonium sulfate crystallization kettle at high temperature for cooling and crystallization, and the crude product ammonium sulfate is obtained by centrifugal separation. ; The separation liquid is returned to the concentration system to concentrate;
  • Step 9 the cooling liquid in the crystallization kettle is separated by a centrifuge, and the by-product urea sulfate/ammonium sulfate product is separated, and the separated liquid is returned to the concentration kettle to continue to concentrate;
  • Step 10 When the concentration kettle is heated to 100°C, a large amount of water is distilled out, and part of it is separated into condensed water by the tower, which is sent to the wastewater treatment system for treatment, and part of the water vapor is discharged.

Abstract

本发明公开了一种DL-对羟基苯海因及其硫酸脲/硫酸铵生产工艺，包括以下步骤：步骤1、将苯酚、尿素、硫酸按照摩尔比加入到反应釜中，缓慢升温，控制反应温度在70-95℃，保温30min；步骤2、向步骤1反应液中滴加乙醛酸，滴加时间控制在2-8h；步骤3、滴加反应结束后，控制反应釜内温度不低于85℃，保温2-5h后放料；本发明的有益效果是：本发明工艺与盐酸法合成DL-对羟基苯海因产品相比，产品质量和收率均有提高，解决了盐酸法合成DL-对羟基苯海因产品过程中，生产现场有大量HCL气体放出，以及废盐酸等其它有机物对生产环境和生产设备产生的影响。

Description

一种DL-对羟基苯海因及其硫酸脲/硫酸铵生产工艺 技术领域
本发明涉及DL-对羟基苯海因技术领域，具体为一种DL-对羟基苯海因及其硫酸脲/硫酸铵生产工艺。
 背景技术
目前，国内DL-对羟基苯海因生产工艺全部采用盐酸法合成工艺路线，该生产工艺存在有以下缺陷:1、生产过程中产生大量有害的HCL气体，对生产环境和生产设备产生影响，需要用吸附塔净化处理:2、废水处理过程中产生大量的固体危废，需要由专门的危废处理公司处理，成本高:3、生产设备易腐蚀，维护成本高:4、成品中的副产物含量偏高。采用盐酸法合成工艺路线的最大缺点就是产生固废量大、废水处理困难、成本高，特别是生产过程中产生的大量固废已成为影响企业正常生产的最大障碍。
 技术解决方案
本发明的目的是克服盐酸法生产DL-对羟基苯海因的工艺缺陷，解决上述生产工艺中三废处理困难、产生固废量大、成本高的难题。本发明以乙醛酸、苯酚、尿素、硫酸为原料，按一定的摩尔比，经缩合、抽滤、离心水洗、干燥得到DL-对羟基苯海因产品。生产母液经高温浓缩分解、加压蒸馏去除有机产物，再加入一定量的氨水中和，经反应、冷却、结晶、分离，生产出符合国内复合肥生产使用的硫酸脲/硫酸铵产品。
为实现上述目的，本发明提供如下技术方案：一种DL-对羟基苯海因及其硫酸脲/硫酸铵生产工艺，包括以下步骤：
步骤1、将苯酚、尿素、硫酸按照摩尔比加入到反应釜中，缓慢升温，控制反应温度在70-95℃，保温30min；
步骤2、向步骤1反应液中滴加乙醛酸，滴加时间控制在2-8h；
步骤3、滴加反应结束后，控制反应釜内温度不低于85℃，保温2-5h后放料；
步骤4、将反应釜中物料放入准备好的过滤器中，抽滤至物料表面无肉眼可见水滴后，再将物料趁热移至准备好的离心机中；
步骤5、向离心机中放入准备好的不低于85℃的热水，溢过物料表面，离心洗涤3次后将物料包装好送至烘干，经烘干至含水量不高于0.5％，包装成品；
步骤6、将过滤母液和洗涤水合并收集，部分转至步骤1使用，剩余部分转至母夜浓缩，回收硫酸脲/硫酸铵产品；
步骤7、将回收母液加入浓缩釜中，控制浓缩釜内温度不高于115℃，根据实际情况控制蒸馏时间，然后收集蒸馏液；
步骤8、在调节池内向母液内加入氨水调节PH值范围至1-5.5，然后将其加入浓缩釜内浓缩，浓缩后浓缩液高温打入硫酸铵结晶釜冷却结晶，通过离心分离得粗品硫酸铵；分离液回浓缩系统浓缩；
步骤9、将浓缩釜内冷却液放入结晶釜内冷却液离心机分离，分离出副产品硫酸脲/硫酸铵产品，分离液回浓缩釜继续浓缩；
步骤10：浓缩釜加热至100℃时，大量水蒸出，通过塔分离部分成冷凝水，送入废水处理系统进行处理，部分水蒸气排放。
作为优选，所述步骤1中苯酚:尿素:硫酸的摩尔比为(0.5-1.0):(0.9-1.3):(0.9-1.3)。
作为优选，所述步骤1中的催化剂为浓度为36-75％硫酸。
作为优选，所述步骤2中滴加浓度为40-75％乙醛酸的量为1.0-1.4摩尔。
作为优选，所述步骤6至步骤9使用硫酸做催化剂后，在浓缩液中加入氨水中和。
作为优选，所述步骤8中，所述浓缩釜内温度不高于115℃，反应后冷却至常温。
作为优选，所述步骤9中，分离液回浓缩釜继续浓缩处理，经处理合格后排放。
作为优选，所述步骤6中硫酸脲的含量为8-12％，且硫酸铵的含量为85-95％。
 有益效果
与现有技术相比，本发明的有益效果是：本发明工艺与盐酸法合成DL-对羟基苯海因产品相比，产品质量和收率均有提高，解决了盐酸法合成DL-对羟基苯海因产品过程中，生产现场有大量HCL气体放出，以及废盐酸等其它有机物对生产环境和生产设备产生的影响，同时有效解决了盐酸法合成DL-对羚基苯海因生产过程中产生的固废量大、废水处理困难、成本高的难题，可以降低90%以上的固废产生；同时本发明回收的硫酸脲/硫酸铵副产品可以直接用于复合肥生产，既降低了废水处理成本，又增加了经济效益；生产过程中产生的废水经微电解、过滤树脂吸驸、絮凝脱色、反渗透膜过滤后可以实现达标排放。
 附图说明
图1为本发明硫酸法合成DL-对羟基苯海因生产工艺流程图；
图2为本发明的DL-对羟基苯海因主反应化学式；
图3为本发明的DL-对羟基苯海因副反应化学式。
 本发明的实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
请参阅图1-3，本发明提供一种技术方案：一种DL-对羟基苯海因及其硫酸脲/硫酸铵生产工艺，包括以下步骤：
步骤1、将苯酚、尿素、硫酸按照摩尔比加入到反应釜中，缓慢升温，控制反应温度在70-95℃，保温30min；
步骤2、向步骤1反应液中滴加乙醛酸，滴加时间控制在2-8h；
步骤3、滴加反应结束后，控制反应釜内温度不低于85℃，保温2-5h后放料；
步骤4、将反应釜中物料放入准备好的过滤器中，抽滤至物料表面无肉眼可见水滴后，再将物料趁热移至准备好的离心机中；
步骤5、向离心机中放入准备好的不低于85℃的热水，溢过物料表面，离心洗涤3次后将物料包装好送至烘干，经烘干至含水量不高于0.5％，包装成品；
步骤6、将过滤母液和洗涤水合并收集，部分转至步骤1使用，剩余部分转至母夜浓缩，回收硫酸脲/硫酸铵产品；
步骤7、将回收母液加入浓缩釜中，控制浓缩釜内温度不高于115℃，根据实际情况控制蒸馏时间，然后收集蒸馏液；
步骤8、在调节池内向母液内加入氨水调节PH值范围至1-5.5，然后将其加入浓缩釜内浓缩，浓缩后浓缩液高温打入硫酸铵结晶釜冷却结晶，通过离心分离得粗品硫酸铵；分离液回浓缩系统浓缩；
步骤9、将浓缩釜内冷却液放入结晶釜内冷却液离心机分离，分离出副产品硫酸脲/硫酸铵产品，分离液回浓缩釜继续浓缩；
步骤10：浓缩釜加热至100℃时，大量水蒸出，通过塔分离部分成冷凝水，送入废水处理系统进行处理，部分水蒸气排放。
其中，所述步骤1中苯酚:尿素:硫酸的摩尔比为(0.5-1.0):(0.9-1.3):(0.9-1.3)。
其中，所述步骤1中的催化剂为浓度为36-75％硫酸。
其中，所述步骤2中滴加浓度为40-75％乙醛酸的量为1.0-1.4摩尔。
其中，所述步骤6至步骤9使用硫酸做催化剂后，在浓缩液中加入氨水中和。
其中，所述步骤8中，所述浓缩釜内温度不高于115℃，反应后冷却至常温
其中，所述步骤9中，分离液回浓缩釜继续浓缩处理，经处理合格后排放。
其中，所述步骤6中硫酸脲的含量为8-12％，且硫酸铵的含量为85-95％。
实施例1：
在装有机械搅拌、回流冷凝管、温度计、滴液漏斗的250mL四口烧瓶中，依次加入尿素37g、苯酚20g、浓度为75％的硫酸40mL，在搅拌状况下，控制反应温度在80℃，缓慢滴加称量好的40%乙醛酸溶液30g，控制滴加时间4h左右，反应温度不低于85℃；滴加反应结束后，再保温搅拌30min，将反应液冷却至室温，析出白色结晶物；用布氏漏斗抽滤，滤饼用50mL不低于85℃的热水洗涤3次，抽滤至滤饼表面无游离水分后，将滤饼放入干燥箱中干燥至含水量不高于0.5％，得到DL-对羟基苯海因25g，纯度98.5%以上，质量收率（以苯酚计）85%。
实施例2：
在装有机械搅拌、温度计、滴液漏斗的2000mL烧杯中，反应母液200mL，再依次加入尿素150g、苯酚73g、浓度为36％的硫酸125mL，在搅拌状况下，控制反应温度在85℃，缓慢滴加称量好的40%乙醛酸溶液110g，控制滴加时间4h左右，反应温度不低于85℃；滴加反应结束后，再保温搅拌30min，将反应液冷却至室温，析出白色结晶物；用布氏漏斗抽滤，滤饼用150mL不低于85℃的热水洗涤3次，抽滤至滤饼表面无游离水分后，将滤饼放入干燥箱中干燥至含水量不高于0.5％，得到DL-对羟基苯海因92g，纯度98.5%以上，质量收率（以苯酚计）85%。
实施例3：
步骤1、在2000L搪瓷反应釜中，反应母液500L，开启搅拌，再依次向反应釜中加入尿素250Kg、苯酚170Kg、浓度为60％的硫酸180L，缓慢控制反应温度在90℃，保温30min；
步骤2、保温结束后，向反应釜中滴加称量好的50%乙醛酸255Kg，控制釜内反应温度不超过90℃，滴加时间不低于4h；
步骤3、滴加反应结束后，控制反应温度不低于85℃，保温30min；然后降温至85℃，准备放料；
步骤4、将反应釜中物料放入准备好的过滤器中，抽滤至物料表面无肉眼可见水滴后，再趁热将物料移至准备好的离心机中；
步骤5、向离心机中放入准备好的不低于85℃的热水，溢过物料表面，离心洗涤3次后将物料包装好送至烘干，经烘干至含水量不高于0.5％，包装成品；
步骤6、将过滤母液和洗涤水合并收集，一部分转至步骤1使用，剩余部分转至母液浓缩，回收硫酸脲/硫酸铵产品；
步骤7、将回收母液加入浓缩釜中，控制浓缩釜内温度不低于115℃，蒸馏4h，收集蒸馏液；
步骤8、在调节池内向母液内加入氨水调节PH值范围至1-5.5，然后将其加入浓缩釜内浓缩，浓缩后浓缩液高温打入硫酸铵结晶釜冷却结晶，通过离心分离得粗品硫酸铵；分离液回浓缩系统浓缩；
步骤9、将结晶釜内冷却液通过离心机分离，分离出副产品硫酸脲/硫酸铵产品，分离液回浓缩釜继续浓缩；
步骤10：浓缩釜加热至100℃时，大量水蒸出，通过塔分离部分成冷凝水，送入废水处理系统进行处理，部分水蒸气排放。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。

Claims (8)

  1. 一种DL-对羟基苯海因及其硫酸脲/硫酸铵生产工艺，其特征在于：包括以下步骤：步骤1、将苯酚、尿素、硫酸按照摩尔比加入到反应釜中，缓慢升温，控制反应温度在70-95℃，保温30min；步骤2、向步骤1反应液中滴加乙醛酸，滴加时间控制在2-8h；步骤3、滴加反应结束后，控制反应釜内温度不低于85℃，保温2-5h后放料；步骤4、将反应釜中物料放入准备好的过滤器中，抽滤至物料表面无肉眼可见水滴后，再将物料趁热移至准备好的离心机中；步骤5、向离心机中放入准备好的不低于85℃的热水，溢过物料表面，离心洗涤3次后将物料包装好送至烘干，经烘干至含水量不高于0.5％，包装成品；步骤6、将过滤母液和洗涤水合并收集，部分转至步骤1使用，剩余部分转至母夜浓缩，用于回收硫酸脲/硫酸铵产品；步骤7、将回收母液加入浓缩釜中，控制浓缩釜内温度不高于115℃，根据实际情况控制蒸馏时间，然后收集蒸馏液；步骤8、在调节池内向母液内加入氨水调节PH值范围至1-5.5，然后将其加入浓缩釜内浓缩，浓缩后浓缩液高温打入硫酸铵结晶釜冷却结晶，通过离心分离得粗品硫酸铵；分离液回浓缩系统浓缩；步骤9：浓缩釜加热至100℃时，大量水蒸出，通过塔分离部分成冷凝水，送入废水处理系统进行处理，部分水蒸气排放。
  2. 根据权利要求1所述的一种DL-对羟基苯海因及其硫酸脲/硫酸铵生产工艺，其特征在于：所述步骤1中苯酚:尿素:硫酸的摩尔比为(0.5-1.0):(0.9-1.3):(0.9-1.3)。
  3. 根据权利要求2所述的一种DL-对羟基苯海因及其硫酸脲/硫酸铵生产工艺，其特征在于：所述步骤1中的催化剂为浓度为36-75％硫酸。
  4. 根据权利要求3所述的一种DL-对羟基苯海因及其硫酸脲/硫酸铵生产工艺，其特征在于：所述步骤2中滴加浓度为40-75％乙醛酸的量为1.0-1.4摩尔。
  5. 根据权利要求4所述的一种DL-对羟基苯海因及其硫酸脲/硫酸铵生产工艺，其特征在于：所述步骤6至步骤9使用硫酸做催化剂后，在浓缩液中加入氨水中和。
  6. 根据权利要求1所述的一种DL-对羟基苯海因及其硫酸脲/硫酸铵生产工艺，其特征在于：所述步骤8中，所述浓缩釜内温度不高于115℃，反应后冷却至常温。
  7. 根据权利要求1所述的一种DL-对羟基苯海因及其硫酸脲/硫酸铵生产工艺，其特征在于：所述步骤9中，分离液回浓缩釜继续浓缩处理，经处理合格后排放。
  8. 根据权利要求1所述的一种DL-对羟基苯海因及其硫酸脲/硫酸铵生产工艺，其特征在于：所述步骤6中硫酸脲的含量为8-12％，且硫酸铵的含量为85-95％。
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