WO2015149586A1 - 一种tbhq的制备工艺 - Google Patents

一种tbhq的制备工艺 Download PDF

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WO2015149586A1
WO2015149586A1 PCT/CN2015/072388 CN2015072388W WO2015149586A1 WO 2015149586 A1 WO2015149586 A1 WO 2015149586A1 CN 2015072388 W CN2015072388 W CN 2015072388W WO 2015149586 A1 WO2015149586 A1 WO 2015149586A1
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tbhq
weight
parts
hours
heating
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PCT/CN2015/072388
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French (fr)
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卢俊青
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广州泰邦食品科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/685—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation

Definitions

  • the invention relates to the technical field of production of TBHQ, in particular to a preparation process of TBHQ.
  • Grease and fat-rich products often undergo oxidative deterioration during storage and transportation. After oxidation, the product undergoes discoloration, produces odor, and destroys the nutrients therein, while generating harmful substances, which seriously degrades the product grade. In order to prevent or delay the occurrence of these conditions, it is common practice to add antioxidant components to them. As approved by FAO/WHO, the currently available synthetic antioxidants for food are mainly BHT, BHA, PG, TBHQ and the like.
  • BHT is cheap, but it is very toxic; BHA has also been found to be carcinogenic in recent years, and many countries have begun to ban; PG toxicity is small, and the main raw materials are natural, the potential danger is relatively small, but it is easy to be with the metal in the product. Ions combine to reveal color, which destroys the original color of the product.
  • TBHQ does not have the defects of the above varieties, its safety has been evaluated by FAO and WHO, and it belongs to the safety A (I) category [2], and TBHQ has special effects on antioxidants of vegetable oils, and also has good anti-bacteria, The ability of mold and yeast is a highly effective new edible antioxidant.
  • TBHQ is a product obtained by alkylation of hydroquinone with an alkylating agent.
  • some companies use toluene as a solvent to synthesize TBHQ.
  • the crude TBHQ obtained by this method has high purity of TBHQ.
  • toluene is used as a solvent in the synthesis process, in the TBHQ product obtained, inevitable toluene remains.
  • the product will have black or black spots after being placed for a certain period of time, and the toluene remaining in the synthesis process and after completion cannot be discharged into the water according to environmental protection regulations, which will cause soil pollution and can only be evaporated.
  • an object of the present invention is to provide a process for preparing TBHQ, which can produce high-purity TBHQ while avoiding environmental pollution, and has high utilization rate of raw materials.
  • the technical solution of the present invention is:
  • a preparation process of TBHQ comprising the following steps:
  • reaction product is centrifuged, washed with water, and dehydrated to obtain a crude TBHQ;
  • step 5 The first step of centrifugation of the solution obtained in step 4), separating the water-insoluble DTBHQ from the crude TBHQ, and then cooling the solution. When cooling to below 45 ° C, a second centrifugation is performed. Crystal washing, dehydration, drying, that is, TBHQ boutique;
  • the agitation speed in step 1) is from 55 to 65 rpm.
  • the heating temperature in step 2) is from 58 ° C to 62 ° C.
  • the acid in step 4) is mixed with water and heated to between 84 ° C and 86 ° C.
  • the crude product is added to step 4) and heated to 92 ° C to 93 ° C.
  • the time for natural cooling in step 7) is from 45 hours to 50 hours.
  • the first 12 hours of natural cooling in step 7) should be stirred at least twice.
  • the acid in step 4) is citric acid.
  • the drying temperature in step 5 is from 95 ° C to 105 ° C.
  • the drying in step 7) is: tiling the obtained crystal on a drying tray, tiling a thickness of 4-6 cm, and baking for 8 hours to 16 hours.
  • the TBHQ production process of the present invention uses a hydroformylation reaction of hydroquinone and an alkylating agent, tert-butanol, to obtain a crude TBHQ, which is actually formed by hydration of isobutylene. Therefore, when the isobutylene is used as the alkylating agent, the raw material cost is low, and when the tert-butyl alcohol is used as the alkylating agent, the TBHQ yield is high, and the transportation is convenient, and the storage is easy.
  • the catalyst used in the reaction is phosphoric acid.
  • the formation of disubstituted by-product DTBHQ is controlled by controlling the concentration of phosphoric acid and adding t-butanol.
  • the present invention controls the addition amount of phosphoric acid and t-butanol to 2 to 4 parts by weight of phosphoric acid, 0.1 to 0.4 parts by weight of water, and to benzene. 5-7 parts by weight of diphenol and 7-9 parts by weight of tert-butanol can make the conversion of hydroquinone high, and the concentration ratio of TBHQ to DTBHQ in the reaction mixture is also maintained at a high level.
  • the invention adopts phosphoric acid as a catalyst, has low corrosivity, low requirements on equipment, easy separation of by-products, and can be recycled, and the use cost is low, and the obtained phosphoric acid can be recovered and utilized as fertilizer; the invention adopts water As a solvent, the method of using toluene in the prior art is abandoned, and the raw material selection and ratio, as well as the process route and process parameters are reasonably and effectively set, so that the obtained TBHQ crude product contains more than 99.3% of TBHQ and a small amount of DTBHQ.
  • TBHQ is soluble in water
  • DTBHQ is insoluble in water.
  • the obtained TBHQ crude product can be separated by water extraction, and TBHQ and DTBHQ can be separated, and it is convenient to obtain TBHQ without toluene residue; and the obtained DTBHQ is not Industrial solid waste, which can be used as an anti-aging agent in the rubber industry. Therefore, the method of the present invention has high utilization rate of raw materials; and the obtained TBHQ refined product is purified by appropriate process conditions to obtain higher purity and more cleanliness. Whiter TBHQ products.
  • the TBHQ preparation process of the present invention comprises the following steps:
  • reaction product is centrifuged, washed with water, and dehydrated to obtain a crude TBHQ;
  • step 5 The first step of centrifugation of the solution obtained in step 4), separating the water-insoluble DTBHQ from the crude TBHQ, and then cooling the solution. When cooling to below 45 ° C, a second centrifugation is performed. TBHQ crystal washing, dehydration, drying, that is, TBHQ boutique;
  • hydroquinone is the main material
  • tert-butanol promotes the conversion of hydroquinone to TBHQ
  • the by-product DTBHQ increases, and if the amount of t-butanol added is too small,
  • the present invention can make the by-product DTBHQ relatively small and the unreacted hydroquinone residue less by properly controlling the amount of each raw material formulation.
  • step 4 the acid and water are mixed and heated first, and when a certain temperature is reached, the crude TBHQ is added, and the acid and water are heated together with the crude TBHQ at the beginning, which can make the TBHQ crude product. Rapid dissolution can prevent the TBHQ from being oxidized and affect the quality of the TBHQ boutique.
  • the acid in the step 4) may generally be phosphoric acid or citric acid, wherein citric acid is preferably used, and citric acid is used to make the final product whiter.
  • the mixed solution is filtered by a filter with a filter screen and a heating jacket to prevent crystal precipitation during filtration and cause loss of TBHQ.
  • reaction product is centrifuged, washed with water, and dehydrated to obtain a crude TBHQ;
  • step 5 The first step of centrifuging the solution of step 4), separating the water-insoluble DTBHQ from the crude TBHQ, and then cooling the solution. When cooling to below 45 ° C, a second centrifugation is performed. TBHQ crystal washing, dehydration, drying, that is, TBHQ boutique;
  • the drying in step 5) is: pouring the wet TBHQ boutique into the vibrating sieve and sieving the sieved TBHQ product on the drying tray, the thickness of the tiling is 6 cm, and drying for 9 hours;
  • step 7) is: the obtained crystal is spread on a drying tray, the thickness of the tile is 5 cm, and baking is performed for 8 hours.
  • the TBHQ product was detected in white color, wherein the weight percentage of TBHQ was 99.8%, and the weight percentage of DTBHQ was 0.2%.
  • reaction product is centrifuged, washed with water, and dehydrated to obtain a crude TBHQ;
  • step 5 The first step of centrifuging the solution of step 4), separating the water-insoluble DTBHQ from the crude TBHQ, and then cooling the solution. When cooling to below 45 ° C, a second centrifugation is performed. TBHQ crystal washing, dehydration, drying, that is, TBHQ boutique;
  • the drying in step 5) is: pouring the wet TBHQ fine product into the vibrating sieve and sieving, and splicing the TBHQ fine product on the drying tray, tiling the thickness to 3 cm, and drying for 7 hours;
  • step 7 The drying of step 7) is: the obtained crystal is spread on a drying tray, the thickness of the tile is 5 cm, and baking is performed for 9 hours.
  • the TBHQ product was detected in white color, wherein the weight percentage of TBHQ was 99.9%, and the weight percentage of DTBHQ was 0.1%.
  • reaction product is centrifuged, washed with water, and dehydrated to obtain a crude TBHQ;
  • step 5 The first step of centrifuging the solution of step 4), separating the water-insoluble DTBHQ from the crude TBHQ, and then cooling the solution. When cooling to below 45 ° C, a second centrifugation is performed. TBHQ crystal washing, dehydration, drying, that is, TBHQ boutique;
  • the drying in step 5) is: pouring the wet TBHQ boutique into the vibrating sieve and sieving the sieved TBHQ product on the drying tray, the thickness of the tile is 4 cm, and drying for 8 hours;
  • step 7) is: the obtained crystal is spread on a drying tray, the thickness of the tile is 4 cm, and baking is performed for 8 hours.
  • the TBHQ product was detected in white color, wherein the weight percentage of TBHQ was 99.8%, and the weight percentage of DTBHQ was 0.2%.
  • reaction product is centrifuged, washed with water, and dehydrated to obtain a crude TBHQ;
  • step 5 The first step of centrifuging the solution of step 4), separating the water-insoluble DTBHQ from the crude TBHQ, and then cooling the solution. When cooling to below 45 ° C, a second centrifugation is performed. TBHQ crystal washing, dehydration, drying, that is, TBHQ boutique;
  • the drying in step 5) is: pouring the wet TBHQ fine product into the vibrating sieve and sieving the sieve, and tiling the TBHQ fine product on the drying tray, the thickness of the tiling is 4 cm, and drying for 7 hours;
  • step 7) is: the obtained crystal is spread on a drying tray, the thickness of the tile is 6 cm, and baking is performed for 12 hours.
  • the TBHQ product was detected in white color, wherein the weight percentage of TBHQ was 99.8%, and the weight percentage of DTBHQ was 0.2%.
  • reaction product is centrifuged, washed with water, and dehydrated to obtain a crude TBHQ;
  • step 5 The first step of centrifuging the solution of step 4), separating the water-insoluble DTBHQ from the crude TBHQ, and then cooling the solution. When cooling to below 45 ° C, a second centrifugation is performed. TBHQ crystal washing, dehydration, drying, that is, TBHQ boutique;
  • the drying in step 5) is: pouring the wet TBHQ fine product into the vibrating sieve and sieving, and splicing the TBHQ fine product on the drying tray, tiling the thickness to 3 cm, and drying for 7 hours;
  • step 7 The drying of step 7) is: the obtained crystal is spread on a drying tray, the thickness of the tile is 6 cm, and baking is performed for 13 hours.
  • the TBHQ product was detected in white color, wherein the weight percentage of TBHQ was 99.8%, and the weight percentage of DTBHQ was 0.2%.
  • the TBHQ content was measured according to the detection method of GB26403-2011.
  • the present invention can obtain a TBHQ product with higher purity, cleanerness and whiter color, and the DTBHQ obtained at the same time is not industrial solid waste, which can be used as an anti-aging agent in the rubber industry, and thus the invention
  • the method has high utilization of raw materials.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

一种TBHQ的制备工艺，包括如下步骤：1）将磷酸2–4重量份、水0.1–0.4重量份倒入搅拌缸，再加入对苯二酚5–7重量份搅拌；2）将搅拌后的溶液置入反应釜中加热至55℃～65℃，投加叔丁醇7–9重量份；升温至75℃～85℃，保温2～3小时；3）处理反应产物，得TBHQ粗品；4）将酸1–3重量份、水93–96重量份混合，加热至82℃～88℃时，加入粗品4.5–6.5重量份，加热至92℃～95℃，溶解即完成；5）将溶液进行第一次离心分离、冷却，当冷却到45℃以下时，进行第二次离心分离，将得到的晶体处理后即得TBHQ精品；6）在反应釜中加入25–27重量份的乙醇，再投加80–90重量份的TBHQ精品；7）温度达到85℃～92℃时，保温1小时～2小时，再过滤、冷却、分离，将得到的晶体烘干后即得。

Description

一种TBHQ的制备工艺
本申请要求2014年04月04日提交中国专利局、申请号为201410136302.1、发明名称为“一种TBHQ的制备工艺”的发明专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及一种TBHQ的生产技术领域，尤其涉及一种TBHQ的制备工艺。
背景技术
油脂及富脂产品在贮藏、运输过程中常常发生氧化变质现象。氧化后，产品发生色变，产生异味，并破坏其中的营养成分，同时产生有害物质，严重地降低产品品位。为了阻止或延缓这些情况的发生，通常的做法是在其中添加抗氧成分。经FAO/WHO认可，现行允许作为食品用的合成抗氧剂主要有BHT、BHA，PG，TBHQ等。其中BHT价廉，但毒性大；BHA近年也被发现存在致癌可能，许多国家已开始禁用；PG毒性虽小，且主要原料来自天然，潜在危险性也比较小，但却易与产品中的金属离子结合而显现颜色，从而破坏产品的原呈色。TBHQ则不存在上述品种的缺陷，其安全性已由FAO、WHO评价，属安全A(I)类[2]，而且TBHQ对植物性油脂抗氧化有特效，同时还兼有良好的抗细菌、霉菌、酵母菌的能力，属高效新型食用抗氧剂。
TBHQ是由对苯二酚与烷基化剂经烷基化反应而得到的产物。目前，有企业采用甲苯作为溶剂合成TBHQ，这种方法制得的TBHQ粗品中TBHQ的纯度高，但由于在合成过程中采用甲苯做溶剂，所以得到的TBHQ产品中不可避免的会有甲苯残留，这种产品在放置一定时间后会出现发黑或黑点的问题，而且合成过程中及完成后残留的甲苯根据环境保护的规定，不能往水里排，会造成土壤的污染，只能通过蒸发向空气里排，这样对一线的生产人员造成身体上的伤害；此外，采用甲苯法制得的TBHQ产品中，除TBHQ外，还有一些无法回收利用的工业固体废料，原料利用率低，而且还需考虑治废问题，耗费财力和人力。
由此可见，如何对现有技术改进，提供一种TBHQ的制备工艺，能够在避免对环境造成污染的情况下，制得高纯度的TBHQ，且原料利用率高，这是本领域需要解决的技术问题。
发明内容
为了解决上述现有技术的不足，本发明的目的在于，提供一种TBHQ的制备工艺，能够在避免对环境造成污染的情况下，制得高纯度的TBHQ，且原料利用率高。
为解决以上技术问题，本发明的技术方案是：
一种TBHQ的制备工艺，包括如下步骤：
1)将磷酸2–4重量份、水0.1–0.4重量份倒入搅拌缸中，再向搅拌缸加入对苯二酚5–7重量份进行搅拌；
2)搅拌后将混合溶液置入反应釜中加热至55℃～65℃，再向反应釜投加叔丁醇7–9重量份，升温至75℃～85℃，保温2～3小时进行反应；
3)将反应产物经离心分离、水洗、脱水后即得TBHQ粗品；
4)将酸1–3重量份、水93–96重量份混合后加热，加热至82℃～88℃时，加入步骤3)制得的TBHQ粗品4.5–6.5重量份，边搅拌边加热，加热至92℃～95℃，溶解即完成；
5)对步骤4)得到的溶液进行第一次离心分离，将TBHQ粗品中不溶于水的DTBHQ分离出去，然后将溶液冷却，当冷却到45℃以下时，进行第二次离心分离，将得到的晶体洗涤、脱水、烘干，即得TBHQ精品；
6)在反应釜中加入25–27重量份的乙醇，将80–90重量份的TBHQ精品边搅拌边加热加入到反应釜中，所述乙醇的浓度为85％～95％；
7)当温度达到85℃～92℃时，保温1小时～2小时，使TBHQ精品完全溶解，然后对混合溶液过滤、自然冷却，待TBHQ充分结晶后，进行离心分离，将得到的晶体进行烘干后即得。
优选地，步骤1)中的搅拌速度为55-65转/分钟。
优选地，步骤2)中的加热温度为58℃～62℃。
优选地，步骤4)中的酸和水混合后，加热至84℃～86℃。
优选地，步骤4)中加入粗品后加热至92℃～93℃。
优选地，步骤7)中自然冷却的时间为45小时～50小时。
优选地，步骤7)中自然冷却的前12小时应至少搅拌两次。
优选地，步骤4)中所述酸为柠檬酸。
优选地，步骤5)中的烘干温度为95℃～105℃。
优选地，步骤7)中的烘干为：将得到的晶体平铺在烘干盘上，平铺厚度为4-6厘米，烘烤8小时～16小时。
与现有技术相比，本发明的TBHQ的生产工艺采用对苯二酚与烷基化剂——叔丁醇经烷基化反应而得到TBHQ粗品，叔丁醇实际是由异丁烯水合而成，故使用异丁烯作烷基化剂时原料成本较低，采用叔丁醇作烷基化剂时TBHQ收率较高，且运输方便，贮存较易。反应所使用的催化剂选用磷酸，通过控制磷酸酸浓度和滴加叔丁醇方法来控制二取代副产物DTBHQ的生成，一般来说，反应用酸浓度越高则对苯二酚的转化率越高，但同时反应选择性即反应混合物中TBHQ与DTBHQ的浓度比越低，所以，本发明将磷酸、叔丁醇的添加量控制在磷酸2–4重量份、水0.1–0.4重量份、对苯二酚5–7重量份、叔丁醇7–9重量份，可以使得对苯二酚的转化率高，同时反应混合物中TBHQ与DTBHQ的浓度比也维持在较高水平。此外，本发明采用磷酸作催化剂，腐蚀性低，对设备要求不高，副产物易分离，而且能够循环利用，使用成本较低，得到的废水中磷酸可以回收作为肥料利用；本发明由于采用水作为溶剂，摒弃现有技术采用甲苯的方法，再通过对原料的选择及配比以及工艺路线、工艺参数进行合理有效设置，因而得到的TBHQ粗品中含有占99.3％以上的TBHQ和少量的DTBHQ，TBHQ溶于水，而DTBHQ不溶于水，因而对得到的TBHQ粗品进行水提分离，即可将TBHQ和DTBHQ分离，很方便地就能得到无甲苯残留的TBHQ精品；而同时得到的DTBHQ也并非工业固体废料，其能够可作为抗老化剂用在橡胶行业，因而本发明的方法，原料利用率高；对得到的TBHQ精品再用乙醇以合适的工艺条件进行提纯，得到纯度更高、更加洁净、颜色更白的TBHQ产品。
具体实施方式
为使本发明的技术方案更加清楚，以下结合通过具体的实施例来对本发明进行详细说明。
本发明的TBHQ制备工艺包括如下步骤：
1)将磷酸2–4重量份、水0.1–0.4重量份倒入搅拌缸中，再向搅拌缸加入对苯二酚5–7重量份进行搅拌；
2)搅拌后将混合溶液置入反应釜中加热至55℃～65℃，再向反应釜投加叔丁醇7–9重量份；然后升温至75℃～85℃后，保温2～3小时进行反应；
3)将反应产物经离心分离、水洗、脱水后即得TBHQ粗品；
4)将酸1–3重量份、水93–96重量份混合，然后进行加热，加热至82℃～88℃时，加入步骤3)制得的TBHQ粗品4.5–6.5重量份，边搅拌边加热，加热至92℃～95℃，溶解即完成；
5)对步骤4)得到的溶液进行第一次离心分离，将TBHQ粗品中不溶于水的DTBHQ分离出去，然后将溶液冷却，当冷却到45℃以下时，进行第二次离心分离，将得到的TBHQ晶体洗涤、脱水、烘干，即得TBHQ精品；
6)在反应釜中加入25–27重量份的乙醇，将80–90重量份的TBHQ精品边搅拌边加热加入到反应釜中，所述乙醇的浓度为85％～95％；
7)温度达到85℃～92℃时，保温1小时～2小时，待TBHQ精品完全溶解后，对混合溶液过滤，然后自然冷却，待TBHQ充分结晶后，进行离心分离，将得到的晶体进行烘干后即得TBHQ产品。
其中，对苯二酚为主料，叔丁醇促进对苯二酚转化成TBHQ，而叔丁醇的添加量太多的话，副产物DTBHQ增多，而叔丁醇的添加量太少的话，则会有未反应的对苯二酚残留，本发明通过合理控制各原料配方量，则能够使得副产物DTBHQ相对较少，而未反应的对苯二酚残留又少。
其中，步骤4)中，先将酸和水混合加热，达到一定温度时，再加入TBHQ粗品，相比于一开始就将酸和水和TBHQ粗品一起加热的方式，这样的方式能够使TBHQ粗品快速溶解，可以避免TBHQ被氧化，而影响得到的TBHQ精品的质量。
其中，步骤4)中的酸一般来说可以为磷酸或柠檬酸，其中优选选用柠檬酸，采用柠檬酸，可使最终产品颜色更白。
其中，步骤7)中对混合溶液采用带滤网及加热套的过滤器的进行过滤，可以防止在过滤时有晶体析出，造成TBHQ的流失。
实施例一
本实施例的TBHQ的制备工艺，包括如下步骤：
1)将磷酸2重量份、水0.1重量份倒入搅拌缸中，再向搅拌缸加入对苯二酚5重量份进行搅拌；
2)搅拌后将混合溶液置入反应釜中加热至55℃，再向反应釜投加叔丁醇9重量份；然后升温至75℃后，保温3小时进行反应；
3)将反应产物经离心分离、水洗、脱水后即得TBHQ粗品；
4)将酸2重量份、水93重量份混合，然后进行加热，加热至82℃时，加入TBHQ粗品4.5重量份，边搅拌边加热，加热至92℃，溶解即完成；
5)对步骤4)的溶液进行第一次离心分离，将TBHQ粗品中不溶于水的DTBHQ分离出去，然后将溶液冷却，当冷却到45℃以下时，进行第二次离心分离，将得到的TBHQ晶体洗涤、脱水、烘干，即得TBHQ精品；
其中，步骤5)中的烘干为：将湿的TBHQ精品倒入振动筛分筛，将筛后的TBHQ精品平铺在烘干盘上，平铺厚度为6厘米，烘干9小时；
6)在反应釜中加入27重量份的乙醇，将80重量份的TBHQ精品边搅拌边加热加入到反应釜中，所述乙醇的浓度为95％；
7)温度达到85℃时，保温2小时，待TBHQ精品完全溶解后，对混合溶液过滤，然后自然冷却，在前12小时搅拌两次，待TBHQ充分结晶后，进行离心分离，将得到的晶体进行烘干后即得TBHQ产品。
步骤7)的烘干为：将得到的晶体平铺在烘干盘上，平铺厚度为5厘米，烘烤8小时。
检测得到的TBHQ产品，颜色白，其中TBHQ的重量百分比为99.8％，DTBHQ的重量百分比为0.2％。
实施例二
本实施例的TBHQ的制备工艺，包括如下步骤：
1)将磷酸3重量份、水0.2重量份倒入搅拌缸中，再向搅拌缸加入对苯二酚5重量份进行搅拌；
2)搅拌后将混合溶液置入反应釜中加热至58℃，再向反应釜投加叔丁醇8重量份；然后升温至78℃后，保温3小时进行反应；
3)将反应产物经离心分离、水洗、脱水后即得TBHQ粗品；
4)将酸3重量份、水94重量份混合，然后进行加热，加热至85℃时，加入TBHQ粗品5重量份，边搅拌边加热，加热至94℃，溶解即完成；
5)对步骤4)的溶液进行第一次离心分离，将TBHQ粗品中不溶于水的DTBHQ分离出去，然后将溶液冷却，当冷却到45℃以下时，进行第二次离心分离，将得到的TBHQ晶体洗涤、脱水、烘干，即得TBHQ精品；
其中，步骤5)中的烘干为：将湿的TBHQ精品倒入振动筛分筛，将筛后的TBHQ精品平铺在烘干盘上，平铺厚度为3厘米，烘干7小时；
6)在反应釜中加入25重量份的乙醇，将80重量份的TBHQ精品边搅拌边加热加入到反应釜中，所述乙醇的浓度为85％；
7)温度达到85℃时，保温1小时，待TBHQ精品完全溶解后，对混合溶液过滤，然后自然冷却，在前12小时搅拌两次，待TBHQ充分结晶后，进行离心分离，将得到的晶体进行烘干后即得TBHQ产品。
步骤7)的烘干为：将得到的晶体平铺在烘干盘上，平铺厚度为5厘米，烘烤9小时。
检测得到的TBHQ产品，颜色白，其中TBHQ的重量百分比为99.9％，DTBHQ的重量百分比为0.1％。
实施例三
本实施例的TBHQ的制备工艺，包括如下步骤：
1)将磷酸4重量份、水0.3重量份倒入搅拌缸中，再向搅拌缸加入对苯二酚6重量份进行搅拌；
2)搅拌后将混合溶液置入反应釜中加热至60℃，再向反应釜投加叔丁醇8重量份；然后升温至80℃后，保温2小时进行反应；
3)将反应产物经离心分离、水洗、脱水后即得TBHQ粗品；
4)将酸3重量份、水95重量份混合，然后进行加热，加热至86℃时，加入TBHQ粗品6.5重量份，边搅拌边加热，加热至93℃，溶解即完成；
5)对步骤4)的溶液进行第一次离心分离，将TBHQ粗品中不溶于水的DTBHQ分离出去，然后将溶液冷却，当冷却到45℃以下时，进行第二次离心分离，将得到的TBHQ晶体洗涤、脱水、烘干，即得TBHQ精品；
其中，步骤5)中的烘干为：将湿的TBHQ精品倒入振动筛分筛，将筛后的TBHQ精品平铺在烘干盘上，平铺厚度为4厘米，烘干8小时；
6)在反应釜中加入26重量份的乙醇，将87重量份的TBHQ精品边搅拌边加热加入到反应釜中，所述乙醇的浓度为88％；
7)温度达到91℃时，保温1小时，待TBHQ精品完全溶解后，对混合溶液过滤，然后自然冷却，在前12小时搅拌两次，待TBHQ充分结晶后，进行离心分离，将得到的晶体进行烘干后即得TBHQ产品。
步骤7)的烘干为：将得到的晶体平铺在烘干盘上，平铺厚度为4厘米，烘烤8小时。
检测得到的TBHQ产品，颜色白，其中TBHQ的重量百分比为99.8％，DTBHQ的重量百分比为0.2％。
实施例四
本实施例的TBHQ的制备工艺，包括如下步骤：
1)将磷酸2重量份、水0.1重量份倒入搅拌缸中，再向搅拌缸加入对苯二酚5重量份进行搅拌；
2)搅拌后将混合溶液置入反应釜中加热至63℃，再向反应釜投加叔丁醇8重量份；然后升温至84℃后，保温2小时进行反应；
3)将反应产物经离心分离、水洗、脱水后即得TBHQ粗品；
4)将酸2重量份、水93重量份混合，然后进行加热，加热至88℃时，加入TBHQ粗品5重量份，边搅拌边加热，加热至95℃，溶解即完成；
5)对步骤4)的溶液进行第一次离心分离，将TBHQ粗品中不溶于水的DTBHQ分离出去，然后将溶液冷却，当冷却到45℃以下时，进行第二次离心分离，将得到的TBHQ晶体洗涤、脱水、烘干，即得TBHQ精品；
其中，步骤5)中的烘干为：将湿的TBHQ精品倒入振动筛分筛，将筛后的TBHQ精品平铺在烘干盘上，平铺厚度为4厘米，烘干7小时；
6)在反应釜中加入27重量份的乙醇，将82重量份的TBHQ精品边搅拌边加热加入到反应釜中，所述乙醇的浓度为90％；
7)温度达到86℃时，保温2小时，待TBHQ精品完全溶解后，对混合溶液过滤，然后自然冷却，在前12小时搅拌两次，待TBHQ充分结晶后，进行离心分离，将得到的晶体进行烘干后即得TBHQ产品。
步骤7)的烘干为：将得到的晶体平铺在烘干盘上，平铺厚度为6厘米，烘烤12小时。
检测得到的TBHQ产品，颜色白，其中TBHQ的重量百分比为99.8％，DTBHQ的重量百分比为0.2％。
实施例五
本实施例的TBHQ的制备工艺，包括如下步骤：
1)将磷酸4重量份、水0.2重量份倒入搅拌缸中，再向搅拌缸加入对苯二酚7重量份进行搅拌；
2)搅拌后将混合溶液置入反应釜中加热至55℃，再向反应釜投加叔丁醇9重量份；然后升温至81℃后，保温2小时进行反应；
3)将反应产物经离心分离、水洗、脱水后即得TBHQ粗品；
4)将酸3重量份、水94重量份混合，然后进行加热，加热至83℃时，加入TBHQ粗品4.5重量份，边搅拌边加热，加热至93℃，溶解即完成；
5)对步骤4)的溶液进行第一次离心分离，将TBHQ粗品中不溶于水的DTBHQ分离出去，然后将溶液冷却，当冷却到45℃以下时，进行第二次离心分离，将得到的TBHQ晶体洗涤、脱水、烘干，即得TBHQ精品；
其中，步骤5)中的烘干为：将湿的TBHQ精品倒入振动筛分筛，将筛后的TBHQ精品平铺在烘干盘上，平铺厚度为3厘米，烘干7小时；
6)在反应釜中加入25重量份的乙醇，将87重量份的TBHQ精品边搅拌边加热加入到反应釜中，所述乙醇的浓度为87％；
7)温度达到88℃时，保温1小时，待TBHQ精品完全溶解后，对混合溶液过滤，然后自然冷却，在前12小时搅拌两次，待TBHQ充分结晶后，进行离心分离，将得到的晶体进行烘干后即得TBHQ产品。
步骤7)的烘干为：将得到的晶体平铺在烘干盘上，平铺厚度为6厘米，烘烤13小时。
检测得到的TBHQ产品，颜色白，其中TBHQ的重量百分比为99.8％，DTBHQ的重量百分比为0.2％。
以上实施例中，按GB26403-2011的检测方法检测TBHQ含量。
由以上实施例可知，本发明能够得到纯度更高、更加洁净、颜色更白的TBHQ产品，而同时得到的DTBHQ也并非工业固体废料，其能够可作为抗老化剂用在橡胶行业，因而本发明的方法，原料利用率高。
以上仅是本发明的优选实施方式，应当指出的是，上述优选实施方式不应视为对本发明的限制，本发明的保护范围应当以权利要求所限定的范围为准。对于本技术领域的普通技术人员来说，在不脱离本发明的精神和范围内，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

  1. 一种TBHQ的制备工艺，其特征在于，包括如下步骤：
    1)将磷酸2–4重量份、水0.1–0.4重量份倒入搅拌缸中，再向搅拌缸加入对苯二酚5–7重量份进行搅拌；
    2)搅拌后将混合溶液置入反应釜中加热至55℃～65℃，再向反应釜投加叔丁醇7–9重量份，升温至75℃～85℃，保温2～3小时进行反应；
    3)将反应产物经离心分离、水洗、脱水后即得TBHQ粗品；
    4)将酸1–3重量份、水93–96重量份混合后加热，加热至82℃～88℃时，加入步骤3)制得的TBHQ粗品4.5–6.5重量份，边搅拌边加热，加热至92℃～95℃，溶解即完成；
    5)对步骤4)得到的溶液进行第一次离心分离，将TBHQ粗品中不溶于水的DTBHQ分离出去，然后将溶液冷却，当冷却到45℃以下时，进行第二次离心分离，将得到的晶体洗涤、脱水、烘干，即得TBHQ精品；
    6)在反应釜中加入25–27重量份的乙醇，将80–90重量份的TBHQ精品边搅拌边加热加入到反应釜中，所述乙醇的浓度为85％～95％；
    7)当温度达到85℃～92℃时，保温1小时～2小时，使TBHQ精品完全溶解，然后对混合溶液过滤、自然冷却，待TBHQ充分结晶后，进行离心分离，将得到的晶体进行烘干后即得。
  2. 如权利要求1所述的TBHQ的制备工艺，其特征在于，步骤1)中的搅拌速度为55-65转/分钟。
  3. 如权利要求1所述的TBHQ的制备工艺，其特征在于，步骤2)中的加热温度为58℃～62℃。
  4. 如权利要求1所述的TBHQ的制备工艺，其特征在于，步骤4)中的酸和水混合后，加热至84℃～86℃。
  5. 如权利要求1所述的TBHQ的制备工艺，其特征在于，步骤4)中加入TBHQ粗品后加热至92℃～93℃。
  6. 如权利要求1所述的TBHQ的制备工艺，其特征在于，步骤7)中自然冷却的时间为45小时～50小时。
  7. 如权利要求1所述的TBHQ的制备工艺，其特征在于，步骤7)中自然冷却的前12小时应至少搅拌两次。
  8. 如权利要求1所述的TBHQ的制备工艺，其特征在于，步骤4)中所述酸为柠檬酸。
  9. 如权利要求1所述的TBHQ的制备工艺，其特征在于，步骤5)中的烘干温度为95℃～105℃。
  10. 如权利要求6所述的TBHQ的制备工艺，其特征在于，步骤7)中的烘干为：将得到的晶体平铺在烘干盘上，平铺厚度为4-6厘米，烘烤8小时～16小时。
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