CN112341571B - Hydrogenation method of terpene resin - Google Patents

Hydrogenation method of terpene resin Download PDF

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Publication number
CN112341571B
CN112341571B CN202011297129.5A CN202011297129A CN112341571B CN 112341571 B CN112341571 B CN 112341571B CN 202011297129 A CN202011297129 A CN 202011297129A CN 112341571 B CN112341571 B CN 112341571B
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resin
parts
hydrogenation
catalyst
cyclohexane
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CN112341571A (en
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李争奎
胡道轲
裴存章
张鹏超
赵艳明
高鹏
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Puyang Xinyu Petrochemical Industry Co ltd
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Abstract

The invention discloses a method for hydrogenating terpene resin, which comprises the steps of firstly carrying out resin synthesis, and activating a hydrogenation catalyst in a first fixed bed hydrogenation reactor and a second fixed bed hydrogenation reactor; feeding cyclohexane solvent into a reactor at a speed of 0.1-5 ml/min, adjusting the introduction speed of hydrogen to 300-400 ml/min, changing the cyclohexane solvent into the molecular sieve dehydration reaction liquid obtained in the step 1) after liquid materials exist in the product liquid separation tank, and reacting to obtain hydrogenated terpene resin to obtain the terpene hydrogenated resin. The invention can reduce the production cost, has low reaction temperature, improves the reaction efficiency, and has the advantages of stable performance, difficult color change and the like of the obtained hydrogenated terpene resin.

Description

Hydrogenation method of terpene resin
Technical Field
The invention belongs to the field of turpentine deep processing, and particularly relates to a hydrogenation method for terpene resin.
Background
The terpene resin is an excellent tackifier, is an important material of the adhesive, and plays a key role in the performance and quality of the adhesive. The terpene resin polymer contains double bonds, so that the terpene resin polymer can change color after absorbing oxygen, the appearance and the quality of products are influenced, and the terpene resin polymer has certain influence on heating resistance and weather resistance. Meanwhile, in terpene resin polymerization, aluminum trichloride is generally used as a catalyst, chloride ions are easily introduced into the resin to cause the quality reduction of the resin, and in order to further improve the quality of the terpene resin, remove impurities in the terpene resin, enhance the stability of the terpene resin and reduce the color of the terpene resin, hydrogenation is needed to be performed on the terpene resin, and the chloride ions, oxygen-containing compounds, sulfides and other impurities in the terpene resin are removed, so that unsaturated bonds in the resin are changed into saturated bonds, the stability of the resin is improved, and the compatibility and the adhesive force of the terpene resin are increased. However, the softening point of the finished product is greatly reduced (about 5-10 ℃) due to high reaction temperature in the conventional hydrogenation of terpene resin, and the terpene resin reaction belongs to polymerization reaction, and if the softening point is reduced, molecular chain breakage exists. Resulting in product loss and reduced product quality. Higher softening points require more molecular polymerization and result in more by-products. The yield of the product is reduced. Greatly influences the polymerization degree and viscosity of the product, and the loss of the fluidized bed or kettle type reactor hydrogenation catalyst is more, about 3 kg/ton resin, greatly increases the cost for producing the terpene resin.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a hydrogenation method for terpene resin, which aims to solve the problems that the hydrogenation process in the prior art can lose more softening points and can not be used for producing high-softening-point resin; fluidized bed reactor or kettle reactor, and serious catalyst loss.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for hydrogenating terpene resin is designed, and comprises the following steps:
1) resin synthesis: adding 20-50% of cyclohexane and a resin synthesis catalyst into a reaction kettle, dropwise adding turpentine and the rest part of cyclohexane into the reaction kettle within 30-90 min, preserving heat for 1-3 hours after dropwise adding, adding water into the reaction kettle after heat preservation, stirring, standing, draining water at the lower part, and dehydrating by using a molecular sieve to obtain a molecular sieve dehydrated reaction solution;
2) activation of a hydrogenation catalyst: placing a hydrogenation catalyst into a first fixed bed hydrogenation reactor and a second fixed bed hydrogenation reactor, introducing hydrogen into the reaction kettle, keeping the pressure at 0.1-1.0 MPa, slowly heating to 150-200 ℃, keeping the temperature for less than 1h, then continuously heating to 150-360 ℃, keeping the temperature for 0.5-6 hours, and then completing the activation of the hydrogenation catalyst;
3) hydrogenation process: feeding the cyclohexane solvent into the reactor at a speed of 0.1-5 ml/min, adjusting the introduction speed of hydrogen to 300-400 ml/min, changing the cyclohexane solvent into the molecular sieve dehydration reaction liquid obtained in the step 1) after the liquid material exists in the product liquid separation tank, and reacting to obtain the hydrogenated terpene resin.
Preferably, in the step 1), before adding cyclohexane and a catalyst into the reaction kettle, the temperature of the cooling water in the reaction kettle is adjusted to 0-20 ℃.
Preferably, in step 1), the resin synthesis polymerization raw materials comprise the following raw materials in parts by weight: 100-600 parts of turpentine, 150-700 parts of cyclohexane and 20-40 parts of catalyst.
Preferably, in step 1), the resin synthesis catalyst comprises the following components by weight: 20-70 parts of aluminum trichloride, 1-30 parts of potassium sulfate, 1-30 parts of anhydrous copper sulfate and 1-30 parts of sulfur trioxide.
Preferably, in the step 2), the temperature in the first fixed bed hydrogenation reactor is controlled to be 160-300 ℃, the temperature in the second fixed bed hydrogenation reactor is controlled to be 260-320 ℃, and the pressure in the reactors is kept to be 0.5-8 Mpa.
Preferably, in step 2), the hydrogenation catalyst comprises the following components in percentage by weight: 0.1-8% of palladium, 0.1-20% of tungsten, 0.1-20% of iron, 0.1-20% of molybdenum, 0.1-20% of nickel, 0.1-20% of cobalt, 0.1-20% of copper, 0.1-20% of platinum and the balance of carrier.
Preferably, in the step 2), the specific surface area of the carrier of the hydrogenation catalyst is 120-350 m2The pore volume is 0.4-1.25 ml/g, the pore diameter is 10-1000 angstroms, the particle size is 2-100 mu m, and the particle size of the palladium metal particles is 1-5 nm.
Preferably, in the step 3), after the resin hydrogenation is completed, cyclohexane is used for washing for 30-90 min.
Preferably, the hydrogenated liquid material obtained in the step 3) is taken out, placed in a container at the temperature of 250-300 ℃ and the pressure of 0.01-0.08 MPa for 10-30 min, and cooled to obtain the hydrogenated terpene resin.
Compared with the prior art, the invention has the beneficial technical effects that:
the invention adopts a self-made catalyst fixed bed for hydrogenation, can effectively reduce the hydrogenation pressure and the hydrogenation temperature, can reduce the reduction of the softening point of the resin, and can produce the hydrogenated terpene resin with high softening point.
The catalyst is activated, so that the activity of the catalyst is greatly improved, and the activity of the activated catalyst is improved; meanwhile, the hydrogenation catalyst is activated by adopting the two fixed beds, the different reaction temperatures of the two reactors are controlled, the resin can generate molecular chain scission at high temperature to reduce the soft change point, molecular bonds easy to hydrogenate can be hydrogenated at low temperature, and the rest molecular bonds not easy to hydrogenate can be heated in the second reactor for reaction, so that the high-temperature time is reduced, the production heat source is greatly saved, the hydrogenation pressure and the hydrogenation temperature can be effectively reduced, the reduction of the softening point of the resin can be reduced, and the hydrogenated terpene resin with high softening point can be obtained. Fluidized bed hydrogenation and reaction kettle hydrogenation are conventionally adopted, and because a catalyst and a reaction liquid are mixed together in a fluidized bed reactor, a filter is required for separation, and in the process, the catalyst is broken into smaller particles and cannot be filtered and recovered, so that loss is caused. The catalyst loss is 3 kg/ton resin, while the invention adopts fixed bed hydrogenation, and the fixed bed reactor catalyst is filled in the reactor as a filler, so that the crushing loss is avoided. The cost is saved, namely the cost of the catalyst is saved, the loss of the catalyst can be greatly reduced, the loss of the catalyst is effectively avoided, and the apportionment cost of about 1500 yuan per ton of resin is reduced; moreover, the quality of the fixed bed hydrogenation product is more stable, and the product fluctuation is small. The hydrogenated terpene resin produced by the method has the characteristics of high quality, capability of removing impurities in the hydrogenated terpene resin, reduction of stimulation to human body contact, increase of stability and difficulty in color change. The softening point of a finished product is reduced by about 5-10 ℃ due to high reaction temperature in the conventional terpene resin hydrogenation process, and the process is reduced by 2 ℃.
The invention preferably selects the component content of the hydrogenation catalyst, the specific surface area and the particle size of the catalyst and the aperture of the carrier, so that the hydrogenation catalyst can have better chlorine resistance and better selectivity, olefin saturated impurities are removed in the hydrogenation reaction, and the disconnection of molecular chains is reduced.
The invention preferably selects the composite catalyst consisting of aluminum trichloride, potassium sulfate, anhydrous copper sulfate and sulfur trioxide to have higher activity, the activity of the composite catalyst is higher, the reaction can be effectively accelerated, and the olefin components capable of reacting in the raw materials can react quickly. Meanwhile, a part of materials with low reaction activity in the raw materials can participate in the reaction, so that the conversion rate of olefin in the raw materials can be improved, and the conversion rate can be improved from 90% to 98%.
The invention preferably selects palladium, tungsten, iron, molybdenum, nickel, cobalt, copper and platinum, and the balance is carrier, the combined catalyst can effectively reduce the temperature of hydrogenation reaction, and the temperature of the hydrogenation catalyst is reduced from 300 ℃ to 180 ℃, thereby reducing the loss of softening point of the hydrogenated terpene resin.
The hydrogenated terpene resin produced by the method has the characteristics of high quality, capability of removing impurities in the hydrogenated terpene resin, reduction of stimulation to human body contact, increase of stability and difficulty in color change.
Detailed Description
The following examples are given to illustrate specific embodiments of the present invention, but are only intended to illustrate the present invention in detail and should not be construed as limiting the scope of the present invention in any way. The instruments and devices referred to in the following examples are conventional instruments and devices unless otherwise specified; the raw materials are all conventional commercial raw materials if not specifically stated; the processing and manufacturing methods are conventional methods unless otherwise specified.
Example 1: a method for hydrogenating terpene resin comprises the following steps:
1) resin synthesis: adjusting the temperature of cooling water in a reaction kettle to 20 ℃, adding 30% cyclohexane and a resin synthesis catalyst into the reaction kettle, dropwise adding turpentine and the rest cyclohexane into the reaction kettle within 60min of reaction, preserving heat for 2 hours after dropwise adding, adding water into the reaction kettle after preserving heat, stirring, stopping stirring and standing, discharging water at the lower part, and dehydrating by using a 5-micron molecular sieve to obtain a molecular sieve dehydrated reaction solution; wherein, the resin synthesis polymerization raw materials comprise the following raw materials in parts by weight: 600 parts of turpentine, 700 parts of cyclohexane and 40 parts of catalyst; the resin synthesis catalyst comprises the following components in parts by weight: 70 parts of aluminum trichloride, 10 parts of potassium sulfate, 10 parts of anhydrous copper sulfate and 10 parts of sulfur trioxide;
2) activation of a hydrogenation catalyst: putting a hydrogenation catalyst into 30mL of a first fixed bed hydrogenation reactor and 70mL of a second fixed bed hydrogenation reactor, introducing hydrogen into a reaction kettle, keeping the pressure at 0.1-1.0 MPa, slowly heating to 200 ℃, keeping the temperature for 1h, then continuously heating to 280 ℃, keeping the temperature for two hours, and then completing the activation of the hydrogenation catalyst; controlling the temperature in the first fixed bed hydrogenation reactor to be 160 ℃, the temperature in the second fixed bed hydrogenation reactor to be 260 ℃, and keeping the pressure in the reactors to be 8 Mpa; the hydrogenation catalyst comprises the following components in percentage by weight: 0.1-8% of palladium, 0.1-20% of tungsten, 0.1-20% of iron, 0.1-20% of molybdenum, 0.1-20% of nickel, 0.1-20% of cobalt, 0.1-20% of copper, 0.1-20% of platinum and the balance of carrier; the specific surface area of the carrier of the hydrogenation catalyst is 120-350 m2The specific surface area of the palladium metal particles is 0.4-1.25 ml/g, the pore diameter is 10-1000 angstroms, the particle size is 2-100 mu m, and the particle size of the palladium metal particles is 1-5 nm;
3) a hydrogenation process: feeding a cyclohexane solvent into a reactor at a speed of 1 ml/min, adjusting the introduction speed of hydrogen to 300-400 ml/min, changing the cyclohexane solvent into a molecular sieve dehydrated reaction liquid obtained in the step 1) after a liquid material exists in a product liquid separation tank, and reacting to obtain a hydrogenated liquid material; after the resin hydrogenation is finished, washing for 30min by using cyclohexane; taking out the hydrogenated liquid material obtained in the step 3), placing the hydrogenated liquid material in a container at 250 ℃ and under the pressure of 0.03Mpa for 10min, and cooling to obtain the hydrogenated terpene resin.
Example 2: a method for hydrogenating terpene resin comprises the following steps:
1) resin synthesis: adjusting the temperature of cooling water in a reaction kettle to 10 ℃, adding 35% of cyclohexane and a resin synthesis catalyst into the reaction kettle, dropwise adding turpentine and the rest part of cyclohexane into the reaction kettle within 60min of reaction, preserving heat for 1 hour after dropwise adding, adding water into the reaction kettle after heat preservation, stirring, stopping stirring and standing, discharging the water at the lower part, and dehydrating by using a molecular sieve to obtain a molecular sieve dehydrated reaction solution; wherein, the resin synthesis polymerization raw materials comprise the following raw materials in parts by weight: 500 parts of turpentine, 400 parts of cyclohexane and 30 parts of catalyst; the resin synthesis catalyst comprises the following components in parts by weight: 50 parts of aluminum trichloride, 20 parts of potassium sulfate, 20 parts of anhydrous copper sulfate and 10 parts of sulfur trioxide;
2) activation of a hydrogenation catalyst: putting a hydrogenation catalyst into 30ml of a first fixed bed hydrogenation reactor and 70ml of a second fixed bed hydrogenation reactor, introducing hydrogen into a reaction kettle, keeping the pressure at 0.1-1.0 MPa, slowly heating to 200 ℃, keeping the temperature for 1h, then continuously heating to 280 ℃, keeping the temperature for two hours, and then completing the activation of the hydrogenation catalyst; controlling the temperature in the first fixed bed hydrogenation reactor to be 160 ℃, the temperature in the second fixed bed hydrogenation reactor to be 260 ℃, and keeping the pressure in the reaction kettle to be 8 Mpa; the hydrogenation catalyst comprises the following components in percentage by weight: 0.1-8% of palladium, 0.1-20% of tungsten, 0.1-20% of iron, 0.1-20% of molybdenum, 0.1-20% of nickel, 0.1-20% of cobalt, 0.1-20% of copper, 0.1-20% of platinum and the balance of carrier; the specific surface area of the carrier of the hydrogenation catalyst is 120-350 m2The pore volume is 0.4-1.25 ml/g, the pore diameter is 10-1000 angstroms, the particle size is 2-100 mu m, and the particle size of palladium metal particles is 1-5 nm;
3) hydrogenation process: introducing a cyclohexane solvent into the reactor at a speed of 1.5 ml/min, adjusting the introduction speed of hydrogen to 350 ml/min, changing the cyclohexane solvent into a molecular sieve dehydrated reaction liquid obtained in the step 1) after a liquid material exists in a product liquid separation tank, and reacting to obtain a hydrogenated liquid material; after the resin hydrogenation is finished, washing for 30min by using cyclohexane; taking out the hydrogenated liquid material obtained in the step 3), placing the hydrogenated liquid material in a container at 260 ℃ and under the pressure of 0.08Mpa for 15min, and cooling to obtain the hydrogenated terpene resin.
Example 3: a method for hydrogenating terpene resin comprises the following steps:
1) resin synthesis: adjusting the temperature of cooling water in a reaction kettle to 10 ℃, dropwise adding 30% of cyclohexane and a resin synthesis catalyst in the reaction kettle into the reaction kettle within 45min, preserving heat for 2 hours after dropwise adding, adding water into the reaction kettle after preserving heat, stirring, stopping stirring and standing, discharging water at the lower part, and dehydrating by using a molecular sieve to obtain a molecular sieve dehydrated reaction solution; wherein, the resin synthesis polymerization raw materials comprise the following raw materials in parts by weight: 600 parts of turpentine, 700 parts of cyclohexane and 40 parts of catalyst; the resin synthesis catalyst comprises the following components in parts by weight: 60 parts of aluminum trichloride, 20 parts of potassium sulfate, 10 parts of anhydrous copper sulfate and 10 parts of sulfur trioxide;
2) activation of a hydrogenation catalyst: putting a hydrogenation catalyst into 30ml of a first fixed bed hydrogenation reactor and 70ml of a second fixed bed hydrogenation reactor, introducing hydrogen into a reaction kettle, keeping the pressure at 0.1-1.0 MPa, slowly heating to 200 ℃, keeping the temperature for 1h, then continuously heating to 280 ℃, keeping the temperature for two hours, and then completing the activation of the hydrogenation catalyst; controlling the temperature in the first fixed bed hydrogenation reactor to be 160 ℃, the temperature in the second fixed bed hydrogenation reactor to be 260 ℃, and keeping the pressure in the reaction kettle to be 8 Mpa; the hydrogenation catalyst comprises the following components in percentage by weight: 0.1-8% of palladium, 0.1-20% of tungsten, 0.1-20% of iron, 0.1-20% of molybdenum, 0.1-20% of nickel, 0.1-20% of cobalt, 0.1-20% of copper, 0.1-20% of platinum and the balance of carrier; the specific surface area of the carrier of the hydrogenation catalyst is 120-350 m2The pore volume is 0.4-1.25 ml/g, the pore diameter is 10-1000 angstroms, the particle size is 2-100 mu m, and the particle size of palladium metal particles is 1-5 nm;
3) hydrogenation process: cyclohexane solvent 2 ml; feeding the mixture into a reactor at a speed of one minute, adjusting the introduction speed of hydrogen to be 300-400 ml/minute, changing a cyclohexane solvent into the molecular sieve dehydrated reaction liquid obtained in the step 1) after a liquid material exists in a product liquid separation tank, and reacting to obtain hydrogenated liquid; after the resin hydrogenation is finished, washing for 30min by using cyclohexane; taking out the hydrogenated liquid material obtained in the step 3), placing the hydrogenated liquid material in a container at 250 ℃ and under the pressure of 0.01Mpa for 20min, and cooling to obtain the hydrogenated terpene resin.
Example 4: a method for hydrogenating terpene resin comprises the following steps:
1) resin synthesis: adjusting the temperature of cooling water in a reaction kettle to 10 ℃, adding part of cyclohexane and a resin synthesis catalyst into the reaction kettle, dropwise adding turpentine and the rest of cyclohexane into the reaction kettle within 60min for reaction, preserving heat for 2 hours after dropwise adding, adding water into the reaction kettle after heat preservation, stirring, stopping stirring and standing, draining water at the lower part, and dehydrating by using a molecular sieve to obtain a molecular sieve dehydrated reaction solution; wherein, the resin synthesis polymerization raw materials comprise the following raw materials in parts by weight: 600 parts of turpentine, 700 parts of cyclohexane and 40 parts of catalyst; the resin synthesis catalyst comprises the following components in parts by weight: 60 parts of aluminum trichloride, 10 parts of potassium sulfate, 20 parts of anhydrous copper sulfate and 10 parts of sulfur trioxide;
2) activation of a hydrogenation catalyst: putting a hydrogenation catalyst into 30ml of a first fixed bed hydrogenation reactor and 70ml of a second fixed bed hydrogenation reactor, introducing hydrogen into a reaction kettle, keeping the pressure at 0.1-1.0 MPa, slowly heating to 200 ℃, keeping the temperature for 1h, then continuously heating to 280 ℃, keeping the temperature for two hours, and then completing the activation of the hydrogenation catalyst; controlling the temperature in the first fixed bed hydrogenation reactor to be 160 ℃, the temperature in the second fixed bed hydrogenation reactor to be 260 ℃, and keeping the pressure in the reaction kettle to be 8 Mpa; the hydrogenation catalyst comprises the following components in percentage by weight: 0.1-8% of palladium, 0.1-20% of tungsten, 0.1-20% of iron, 0.1-20% of molybdenum, 0.1-20% of nickel, 0.1-20% of cobalt, 0.1-20% of copper, 0.1-20% of platinum and the balance of carrier; the specific surface area of the carrier of the hydrogenation catalyst is 120-350 m2The pore volume is 0.4-1.25 ml/g, the pore diameter is 10-1000 angstroms, the particle size is 2-100 mu m, and the particle size of palladium metal particles is 1-5 nm;
3) hydrogenation process: cyclohexane solvent 2 ml; feeding the mixture into a reactor at a speed of one minute, adjusting the introduction speed of hydrogen to be 300-400 ml/minute, changing a cyclohexane solvent into the molecular sieve dehydrated reaction liquid obtained in the step 1) after a liquid material exists in a product liquid separation tank, and reacting to obtain hydrogenated liquid; after the resin hydrogenation is finished, washing for 30min by using cyclohexane; taking out the hydrogenated liquid material obtained in the step 3), placing the liquid material into a container at 250 ℃ and under the pressure of 0.08Mpa for 10min, and cooling to obtain the hydrogenated terpene resin.
Example of effects:
the examples 1-4 are used as a test group, a control group adopts a one-stage hydrogenation mode, other steps and indexes are the same as those of the example 1, and the performance verification indexes are shown in the following table 1:
Figure 294628DEST_PATH_IMAGE002
。
as can be seen from the test results of table 1: 1) by adopting a two-stage hydrogenation process, the softening point of the product is reduced slightly (generally 1-2 ℃) before and after hydrogenation, and meanwhile, the viscosity can still be kept high (205-265 mPa & s); 2) the softening point of the product is reduced more (reaching 12 ℃) by adopting a first-stage hydrogenation process, and the viscosity is reduced more (190 mPa & s) at the same time; 3) from the iodine value and the thermal stability, the hydrogenation depth of the resin product adopting the two-stage hydrogenation process is larger than that of the resin product adopting the one-stage hydrogenation process.
Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes in the specific parameters of the embodiments may be made without departing from the spirit of the present invention, and a plurality of specific embodiments are formed, which are common variations of the present invention, and will not be described in detail herein.

Claims (8)

1. A method for hydrogenating terpene resin is characterized by comprising the following steps:
1) resin synthesis: adding 20-50% of cyclohexane and a resin synthesis catalyst into a reaction kettle, dropwise adding turpentine and the rest part of cyclohexane into the reaction kettle within 30-90 min, preserving heat for 1-3 hours after dropwise adding, adding water into the reaction kettle after heat preservation, stirring, standing, draining water at the lower part, and dehydrating by using a molecular sieve to obtain a molecular sieve dehydrated reaction solution;
2) activation of a hydrogenation catalyst: putting a hydrogenation catalyst into a first fixed bed hydrogenation reactor and a second fixed bed hydrogenation reactor, controlling the temperature in the first fixed bed hydrogenation reactor to be 160-300 ℃, controlling the temperature in the second fixed bed hydrogenation reactor to be 260-320 ℃, and keeping the pressure in the reactors to be 0.5-8 Mpa; introducing hydrogen into the reaction kettle, keeping the pressure at 0.1-1.0 MPa, slowly heating to 150-200 ℃, keeping the temperature for 1h, then continuously heating to 150-360 ℃, keeping the temperature for 0.5-6 h, and then completing the activation of the hydrogenation catalyst;
3) hydrogenation process: feeding the cyclohexane solvent into the reactor at a speed of 0.1-5 ml/min, adjusting the introduction speed of hydrogen to 300-400 ml/min, changing the cyclohexane solvent into the molecular sieve dehydration reaction liquid obtained in the step 1) after the liquid material exists in the product liquid separation tank, and reacting to obtain the hydrogenated terpene resin.
2. The method for hydrogenating terpene resins as claimed in claim 1, wherein in step 1), the temperature of the cooling water in the reaction kettle is adjusted to 0-20 ℃ before adding cyclohexane and catalyst into the reaction kettle.
3. The method for hydrogenating terpene resin as claimed in claim 1, wherein the resin synthesis polymerization raw material in step 1) comprises the following raw materials in parts by weight: 100-600 parts of turpentine, 150-700 parts of cyclohexane and 20-40 parts of catalyst.
4. The method for hydrogenating terpene resins according to claim 1, wherein in step 1), the resin synthesis catalyst comprises the following components by weight: 20-70 parts of aluminum trichloride, 1-30 parts of potassium sulfate, 1-30 parts of anhydrous copper sulfate and 1-30 parts of sulfur trioxide.
5. The method for hydrogenating terpene resins according to claim 1, wherein in step 2), the hydrogenation catalyst comprises the following components in percentage by weight: 0.1-8% of palladium, 0.1-20% of tungsten, 0.1-20% of iron, 0.1-20% of molybdenum, 0.1-20% of nickel, 0.1-20% of cobalt, 0.1-20% of copper, 0.1-20% of platinum and the balance of carrier.
6. The process for hydrogenating terpene resins of claim 1, whereinCharacterized in that in the step 2), the specific surface area of the carrier of the hydrogenation catalyst is 120-350 m2The pore volume is 0.4-1.25 ml/g, the pore diameter is 10-1000 angstroms, the particle size is 2-100 mu m, and the particle size of the palladium metal particles is 1-5 nm.
7. The method for hydrogenating the terpene resin as claimed in claim 1, wherein in the step 3), after the hydrogenation of the resin is completed, the resin is washed with cyclohexane for 30-90 min.
8. The method for hydrogenating terpene resins as claimed in claim 1, wherein the hydrogenated liquid material obtained in step 3) is taken out, placed in a container at 250-300 ℃ and 0.01-0.08 Mpa for 10-30 min, and cooled to obtain hydrogenated terpene resins.
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